Preparing polyester block copolymer with excess unreacted lactones to be removed

ABSTRACT

The invention provides methods for the preparation of polyester block copolymers, by reacting crystalline aromatic polyesters with lactones and/or epoxides. By using a slight excess of lactone in the reaction, and a subsequent solid-phase polycondensation reaction, the method generates high-molecular weight block copolymers of low crystallinity. Methods are also provided for generating polyester block copolymers by melt-mixing or kneading polyester block copolymers with epoxides in the solid phase.

BACKGROUND OF THE INVENTION

The present invention No. I relates to an efficient method for thepreparation of a polyester block copolymer which is excellent in heatresistance and hydrolysis resistance, in which lactones areaddition-polymerized onto a crystalline aromatic polyester.

The present invention No. II relates to a method for the preparation ofa polyester block copolymer which is excellent in heat resistance andhydrolysis resistance, and which has a higher molecular weight, in whichthe polyester block copolymer obtained in the present invention No. I isfurther allowed to react in a solid state.

The present invention No. III relates to a polyester block copolymercomposition which is excellent in heat resistance and hydrolysisresistance, color hue, and melt viscosity stability, and a method forthe preparation thereof.

The present invention No. IV relates to a polyester block copolymercomposition which is excellent in heat resistance under a contact with ametal and a polyvinyl chloride (PVC), and relates to a heat-sensitivebody for a heater cable in which polyester block copolymer-based resinis employed.

The present invention Nos. V and VI relate to a polyester blockcopolymer composition which is excellent in a blow-moldability and heatresistance.

The present invention No. VII relates to a polyester block copolymercomposition composed of a crystalline aromatic polyester and lactones,and relates to a method for the preparation thereof, and which isexcellent in a blow-moldability and heat resistance.

BACKGROUND TECHNOLOGY

Prior arts in relation to the present invention Nos. I and II are asfollows.

Many polyester block copolymers possesses a mechanical property such asflexibility, and widely enlarge uses such as parts for cars and electricand electronic parts as a thermoplastic elastomer which is excellent inheat resistance and chemical resistance, which contains a crystallinearomatic polyester unit such as a polybutylene terephthalate unit as ahard segment, and in which crystallinity is lowered by combination of along chain diol with an aromatic dicarboxylic acid in spite of analiphatic polyether such as a poly(alkyleneoxide) glycol, and/or analiphatic polyester such as a polylactone and/or a polyester, and anaromatic polyester.

Hitherto, as a technology for giving flexibility to a crystallinearomatic polyester, JP-B-73004116 Official Gazette states a method forobtaining a block copolymer having a elasticity by reaction of acrystalline aromatic polyester with lactones. The method stated hereinis a first method which shows that a block copolymer can be obtained byan addition reaction of lactones, however, there is nothing described inrelation to an importance of residual unreacted lactone monomers afterthe above-described reaction and a technical effect, and there is alsonothing described in relation to a melting point in the block copolymerobtained.

On the other hand, JP-B-77049037 Official Gazette describes a method forpolymerizing lactones under the presence of a crystalline aromaticpolyester which is in a solid phase. By descriptions, it is shown that amethod in which a reaction is conducted in a melting state has a problemof a remarkable decline in a melting point of the crystalline aromaticpolyester, and it can be solved by conducting a reaction under a solidcondition.

However, it includes a problem that since it is a reaction at a lowtemperature, there is required a long time of period in the reaction,and since productivity is worse, and it lacks practicability.

Further, JP-B-96009661, JP-B-93023289, JP-B-93023290, JP-B-95033434,JP-B-94033435, JP-A-05043666, and JP-A-05043667 Official Gazettes alldescribe a method for allowing to continuously react a crystallinearomatic polyester with lactones, and some of the Gazettes includedescriptions including a step for removing unreacted lactones. Removalof the unreacted lactone described herein has an effect for reducing amonomer smell in the polyester block copolymer and, moreover, byconducting a continuous removal operation, it has an effect for furtherreducing concentration of the unreacted lactones in the polyester blockcopolymer.

Still further, some of the above-described prior arts describe thatthere is included a step for conducting a polycondensation reaction in asolid state, and the polycondensation reaction in a solid state has aneffect for increasing a solution viscosity of a polyester blockcopolymer (P1).

However, all of the prior arts only describe that a thermal propertysuch as a melting point of a resin obtained are decided by raw materialsto be employed, reaction temperature, reaction time of period, andconditions for removing unreacted lactones, and all the prior arts donot describe a technical concept and a specific method for intentionallyimproving the thermal property by increasing the amount of the lactonesto be introduced and by remaining the amount of the unreacted lactones.

In JP-A-02252729 and JP-A-04072325 Official Gazettes, there is describeda method for elevating a melting point of a block copolymer obtained.The JP-A-02252729 Official Gazette describes a method in which there aredissolved a crystalline aromatic polyester and lactones at a lowertemperature, and those have an effect for reducing decompositionreaction by heating, however, there is small an effect for preventing adecline of a melting point, further, occasionally, a reaction time ofperiod unpreferably becomes long. Further, the JP-A-04072325 OfficialGazette describes that the lactones is partially added in advance in ahighly-polymerized state, and elevation of a melting point can beeffectively actualized. However, in spite of an inherent low cost in thelactones, the method partially highly-polymerized in advance includes aproblem of a fair adverse affection to total profitability.

JP-A-61287922 Official Gazette describes that in a method for thepreparation of an elastic polyester by allowing to react a crystallinearomatic polyester with lactones, the method for the preparation of anelastic polyester characterized in that an addition polymerization isconducted by continuously feeding a melted crystalline polyester andlactones into a reaction vessel, and then, those are allowed to reactwith each other in a solid state.

However, even in the method, there are not shown a technical concept anda specific method, etc., that thermal properties are intentionallyelevated by increasing the amount of the lactones and by remaining theamount of unreacted lactones.

As described hereinabove, those have been still insufficient as a methodfor the preparation of a polyester block copolymer having a high meltingpoint and a high molecular weight.

Prior arts in relation to the present invention No. III are as follows.

However, in relation to the polyester block copolymer composed of a hardsegment and a soft segment described in the prior arts for the presentinvention No. I, an industrially-produced polymer is not sufficient inheat resistance and hydrolysis resistance, and, in the case that it isapplied to a melting molding method such as a blow molding and extrusionmolding in which a high melt viscosity is required, there has beencaused a problem that moldability is worse.

Accordingly, as a method for elevating a heat resistance and hydrolysisresistance in a polyester block copolymer, there have been proposed avariety of methods until now. Further, there are proposed methodssimultaneously elevating a melt viscosity in the many proposes. Forexample, JP-B-77030999 and the above-described JP-B-77049037 OfficialGazettes propose a method for increasing a melt viscosity by a solidphase polymerization. However, in the method for increasing a meltviscosity proposed herein, there is required a very long time of periodfor heating and, further, hydrolysis resistance is not improved at all.

JP-B-91077826 Official Gazette proposes a method for melt-mixing amonofunctional epoxy compound with a bifunctional epoxy compound. By themethod, although heat resistance and hydrolysis resistance are elevated,the hydrolysis resistance is not sufficient, an elevation of a meltviscosity is also insufficient.

In order to allow to become sufficient the hydrolysis resistance of thepolyester elastomer obtained by the method, it is required that anexcessive amount of the epoxy compounds are added, resulting in that amelting point lowers, and viscosity change is large in reheating, and itis problematic in molding stability in the case of conducting a moreprecise molding process.

JP-B-92021703, JP-B-89052441, and JP-B-86042930 Official Gazettesdescribe the further addition of a metal salt of a carboxylic acid as anaccelerator in a reaction.

However, melt viscosity in resins obtained herein is not stillsufficient and, it is anxious that such the addition of the metal saltsunpreferably affects to hydrolysis resistance, and it preferably causesto lower a color hue. On the other hand, as a method for improving amelt viscosity stability, JP-B-88031491 Official Gazette proposes amethod of addition of an epoxy compound and carboxylic acids. In themethod, since there are added the carboxylic acids which changehydrolysis resistance to worse, there must be added a large amount ofthe epoxy compounds in order to obtain a sufficient hydrolysisresistance, resulting in that there are caused a cost increase andcrystallinity lowers.

Prior arts in relation to the present invention No. IV are as follows.

In recent years, there have been employed composite materials ofsynthetic resins with metals and PVC in many fields including electriccables. The composite materials are molded by an extrusion moldingmethod or a fusing method, and employed in a variety of uses.

As a use of such the materials, there is a heater cable for an electricblanket and an electric carpet in which heat resistance is required.

Structure of the heater cable, as shown in FIG. 1, is composed of acenter wire 1, a short wire 2, a heating wire 3, a heat-sensitive body4, and an outer cover 5. The heat-sensitive body 4 has a function as afuse.

This functions in order to cut a heater circuit by fusing theheat-sensitive body 4 which fuses at a narrow temperature range whentemperature abnormally elevates, and there have been mainly employed anylon 12 and a nylon 11 until now. Further, a heat-resistible polyesteris employed as the center wire 1, PVC is employed as the outer cover 5,and copper and a copper alloy are employed as the short wire 2 and theheater wire 3.

The heater wire composed of the composite materials are often exposed toheat cycles in view of functions thereof and, if the heat-sensitive body4 is poor in heat resistance, even though exotherm from the heater wire3 is in a normal range, the heater circuit is occasionally cut or,contrarily, a fusing function does not occasionally work even in thecase of abnormal temperature elevation, resulting in that fire accidentis occasionally caused.

Heretofore, there have been mainly employed resins such as the nylon 12and the nylon 11 as the heat-sensitive body 4.

As the resins, although there is employed a resin which is excellent inheat resistance and does not contain an additive, or a resin compositionin which a hindered phenol-based stabilizer is mixed to prevent heatdeterioration, those include many problems.

Prior arts in relation to the present invention Nos. V, VI, and VII areas follows.

As a method for preparing a polyester block copolymer by allowing toreact an aromatic polyester with lactones, there have been known amethod (JP-A-48004116 Official Gazette) by allowing to react acrystalline aromatic polyester with a lactone, a method (JP-A-48004115Official Gazette) by allowing to react a crystalline aromatic polyesterwith a lactone and to chain-extend by allowing to react an initialcopolymer with a multifunctional acylating agent, and a method (theabove-described JP-B-77049037 Official Gazette) for polymerizing thelactones in a solid phase under the presence of a crystalline aromaticpolyester.

Although the polyester block copolymers obtained by the methods haveexcellent rubbery elasticity and excellent weatherability, thecopolymers are insufficient in heat resistance, and include a drawbackthat viscosity, extension, and strength remarkably lower by exposing toa high temperature for a long time of period.

Further, the copolymers do not have a strain-hardening property which isan important property in blow-molding, and there cannot be obtained amolded article having uniform thickness.

Therefore, in order to improve heat resistance and moldability of theabove-described polyester-type block copolymers, there have beenproposed a method (JP-A-58162654 Official Gazette) in which a mono ormore functional epoxy compound is mixed, a method (JP-A-59152947Official Gazette) in which there are formulated a mono or morefunctional epoxy compound and a metal salt of an aliphatic carboxylicacid, and a method (JP-A-59155458 Official Gazette) in which there areformulated a mono or more functional epoxy compound and anethylene-carboxylic acid copolymer. However, melt viscosity isrelatively low in the compositions obtained in the methods.

There have been problems that because it is difficult to obtain a mutualrelationship between a dependence of a melt viscosity upon extensionspeed and a mixing amount of the metal salt of an aliphatic carboxylicacid, and quality cannot be stabilized, and heat resistance lowers, etc.

Recently, as a method for solving all the problems, although there hasbeen proposed a method (JP-A-07331046 Official Gazette) in which thereare formulated two or more functional epoxy compounds and an imidazolecompound, a dependence of a melt viscosity upon extension speed (It iscalled a strain-hardening property, that is, it is a characteristic ofviscosity increase with an increase of an extending speed. Accordingly,a larger hardening property prevents an excessive extension of anextended portion in blow molding owing to a larger viscosity, and anunextended portion is extended owing to a lower viscosity, as a result,uniform thickness is obtained.) is still insufficient. and there cannotbe obtained a molded article having uniform thickness in blow moldingand, further, there has been a problem that discoloration is remarkable.

DISCLOSURE OF THE INVENTION

Purpose of the present invention No. I is to provide a method for thepreparation of a polyester block copolymer from a crystalline aromaticpolyester and, specifically, to provide a method for the preparation ofa polyester block copolymer which has a low crystallinity and a highmelting viscosity and which is excellent in heat resistance,processability, and hydrolysis resistance.

The present inventors, as a result of an investigation of a method forthe preparation of a polyester block copolymer which is excellent inheat resistance, processability, hydrolysis resistance, and a high meltviscosity, found out that in the method for the preparation of apolyester block copolymer (P1) by allowing to react a crystallinearomatic polyester (A1) with lactones, thermal characteristics of thepolyester block copolymer (P1) can be improved by controlling anintroducing amount of lactones (B) with respect to the above-describedcrystalline aromatic polyester (A1) and an amount of unreacted lactonesremained in the polyester block copolymer (P1), and the presentinvention No. I has been completed.

Purpose of the present invention No. II is to provide a method for thepreparation of a high molecular weight polyester block copolymer from acrystalline aromatic polyester and, specifically, to provide a methodfor the preparation of a polyester block copolymer which is low incrystallinity, and which is excellent in heat resistance,processability, hydrolysis resistance, and which has a high meltviscosity and a higher molecular weight.

The present inventors, as a result of an investigation of a method forthe preparation of a polyester block copolymer in which crystallinity islowered in a crystalline aromatic polyester, and which is excellent inheat resistance, processability, hydrolysis resistance, and which has ahigh melt viscosity, found out that in the method for the preparation ofa polyester block copolymer (P1) by allowing to react the crystallinearomatic polyester with lactones, thermal characteristics of thepolyester block copolymer (P1) can be improved by controlling anintroducing amount of unreacted lactones remained in the polyester blockcopolymer (P1) obtained by the reaction and a polyester block copolymer(P′1) obtained through a reaction in a solid phase can be morehighly-polymerized, and the present invention No. II has been completed.

Purpose of the present invention No. III is to provide a polyester blockcopolymer composition and a method for the preparation thereof, which isexcellent in heat resistance, hydrolysis resistance and color hue, andwhich has a high melt viscosity and melt viscosity stability, and whichis appropriate in molding processing.

The present inventors, as a result of an intensive investigation forobtaining a resin composition which is excellent in heat resistance andhydrolysis resistance and a polyester block-based copolymer which has ahigh melt viscosity and a melt viscosity stability and which isappropriate in molding processability, have found that theabove-described problems can be solved by heating under a specifiedcondition after mixing a mono or more functional epoxy compound with thepolyester block copolymer, and the present invention No. III has beencompleted.

Purpose of the present invention No. IV is to solve a problem thatthermal deterioration is accelerated and heat resistance becomesinsufficient by a combined action of a produced copper ion with acovered PVC or hydrochloric acid isolated from the covered PVC becausethe above-described heater cable is exposed to heat cycles andtemperature elevates to approximately 100° C. or so, and theheat-sensitive body such as a nylon 12 and nylon 11 is brought intocontact with copper or a copper alloy which is a short wire or a heatingwire, and those are brought into contact with a PVC cover at a clearancebetween wound short wires.

The present inventors, as a result of an intensive investigation forsolving the problems in the prior arts, have found out that a polyesterblock copolymer composition is not apt to be suffered by a combinedthermal deterioration even under a circumstance in which it is broughtinto contact with a metal such as copper and copper alloy and PVC, thecomposition is excellent in heat resistance and hydrolysis resistance,the composition is obtained by allowing to react a polyester copolymerwith an epoxy compound after mixing a polyester block copolymer with aspecified epoxy compound and a metal complex and heating and kneading,and the present invention No. IV has been completed.

Purpose of the present invention Nos. V, VI, and VII is to provide apolyester block copolymer composition which has an excellentmoldability, excellent heat resistance, and rubbery elasticity, andwhich can be applied to a variety of molding such as blow moldingwithout any problems.

The present inventors, as a result of an intensive investigation, havefound out that a polyester block copolymer composition can solve theabove-described problems by an elevated strain-hardening property, andthe present invention Nos. V and VI have been completed. The polyesterblock copolymer composition is obtained by mixing a polyester blockcopolymer with an epoxy compound, and then, heating and kneading. Thepolyester block copolymer is obtained by copolymerizing through adding amultifunctional compound having three or more carboxylic groups orhydroxyl groups while allowing to react a crystalline aromatic polyesterwith lactones.

The present inventors have found out that a polyester block copolymercomposition can solve the above-described problems by an elevatedstrain-hardening property, and the present invention No. VII have beencompleted. The polyester block copolymer composition is obtained byadding an epoxy compound to a polyester block copolymer and heating in asolid phase. The polyester block copolymer is obtained by adding aspecified amount of an aliphatic or aromatic multifunctional compoundhaving a specified multifunctional group while allowing to react acrystalline aromatic polyester with lactones.

That is, the present invention No. 1 relates to a method for thepreparation of a polyester block copolymer (P1) characterized in that inthe method for the preparation of 100% by weight of the polyester blockcopolymer (P1) by allowing to react A% by weight of a crystallinearomatic polyester (A1) with B% by weight of lactones (B) (proviso thatA+B=100), not less than (B+0.5)% by weight of lactones (B) areintroduced into A% by weight of a crystalline aromatic polyester (A1),and not less than 0.5% by weight of unreacted lactones are remained withrespect to 100% by weight of the polyester block copolymer (P1) afterpreparation of the copolymer.

The present invention No. 2 relates to a method for the preparation of apolyester block copolymer (P1) as described in the present invention No.1, in which not less than (B+2.5)% by weight of the lactones (B) areintroduced and not less than 2.5% by weight of unreacted lactones areremained with respect to 100% by weight of the polyester block copolymer(P1) after preparation of the copolymer.

The present invention No. 3 relates to a method for the preparation of apolyester block copolymer (P1) as described in the present invention No.1 or 2, in which reaction proportion (A)/(B) of the crystalline aromaticpolyester (A1) with respect to the lactones (B) is 95/5-20/80.

The present invention No. 4 relates to a method for the preparation of apolyester block copolymer (P1) as described in any one of the presentinvention Nos. 1-3, in which the unreacted lactones are removed from thepolyester block copolymer (P1) after reaction.

The present invention No. 5 relates to a method for the preparation of apolyester block copolymer (P1) as described in any one of the presentinvention Nos. 1-4, in which the unreacted lactones are continuouslyremoved.

The present invention No. 6 relates to a method for the preparation of apolyester block copolymer (P1) as described in any one of the presentinvention Nos. 1-5, in which the crystalline aromatic polyester (A1) andthe lactones (B) are continuously supplied into a reaction vessel andallowed to addition-polymerize, and the polyester block copolymer (P1)is continuously taken out.

The present invention No. 7 relates to a method for the preparation of apolyester block copolymer (P1) as described in any one of the presentinvention Nos. 1-6, in which the crystalline aromatic polyester (A1) isa polybutylene terephthalate.

The present invention No. 8 relates to a method for the preparation of apolyester block copolymer (P1) as described in any one of the presentinvention Nos. 1-7, in which the lactones (B) are caprolactone.

The present invention No. 9 relates to a method for the preparation of apolyester block copolymer (P′1) having a high molecular weightcharacterized in that after having prepared the polyester blockcopolymer (P1) as described in any one of the present invention Nos.1-8, it is further allowed to react in a solid phase.

The present invention No. 10 relates to a method for the preparation ofa polyester block copolymer (P′1) having a high molecular weight asdescribed in the present invention No 9, in which reaction in a solidphase is continuously conducted.

The present invention No. 11 relates to a polyester block copolymercomposition (R) obtained by thermally-processing a polyester blockcopolymer composition (Q) obtained by melt-mixing 100 parts by weight ofa polyester block copolymer (P) with 0.1-5 parts by weight of an epoxycompound (C) having,one or more epoxy groups under an inert gasatmosphere and not less than 120° C. in a solid phase, and further, at atemperature lower than a melting point of the polyester block copolymercomposition (R) obtained.

The present invention No. 12 relates to a polyester block copolymercomposition (R) as described in the present invention No. 11,characterized in that the polyester block copolymer (P) is a polyesterblock copolymer (P1) obtained by allowing to react a crystallinearomatic polyester (A1) with lactones (B).

The present invention No. 13 relates to a polyester block copolymercomposition (R) as described in the present invention No. 11,characterized in that the polyester block copolymer (P) is a polyesterblock copolymer (P2) obtained by a polycondensation and/or ring-openingpolymerization of monomer components constructing a crystalline aromaticpolyester (A1); monomer components constructing a low crystallinepolyester (A4); an aliphatic polyether (A2); and/or polylactone (A3).

The present invention No. 14 relates to a polyester block copolymercomposition (R) as described in any one of the present invention Nos.11-13, characterized in that the epoxy compound (C) is an epoxy compound(C2) having two or more epoxy groups.

The present invention No. 15 relates to a polyester block copolymercomposition (R) as described in any one of the present invention Nos.11-14 which is obtained by thermally-processing the polyester blockcopolymer composition (Q) at not less than 150° C. and, moreover, at atemperature of 100- to 5° C.-lower than a melting point of the polyesterblock copolymer composition (R).

The present invention No. 16 relates to a polyester block copolymercomposition (R) as described in any one of the present invention Nos.11-15 which is obtained by further thermally-processing the polyesterblock copolymer composition (Q) after preheating at a temperature lessthan a melting point of the polyester block copolymer composition (R)and, moreover, at a temperature of not more than 150° C. The presentinvention No. 17 relates to a polyester block copolymer composition (R)as described in any one of the present invention Nos. 11-16 in whichthere are formulated at least one kind of compounds selected from thegroup consisting of a hindered phenol-based compound, a sulphur-basedcompound, a phosphorus-based compound, a phenyl amine-based compound,and a hindered amine-based compound.

The present invention No. 18 relates to a polyester block copolymercomposition (R) as described in any one of the present invention Nos.11-17, in which an acid value is not more than 0.5 mgKOH/g in thepolyester block copolymer composition (R) and, moreover, a melting point(Tm(R)) of the composition (R) is not less than a 10° C.-lowertemperature than a melting point (Tm(P)) of the polyester blockcopolymer (P) which is a raw material.

Tm(P)−10° C.≦Tm(R)

The present invention No. 19 relates to a polyester block copolymercomposition (R) as described in any one of the present invention Nos.11-18, in which a melt viscosity stability (MI(T, P, t+10)/(MI(T, P, t))is 0.5-2.0 in the polyester block copolymer composition (R).

In the formula, the melt index (MI(T, P, t)) value is a value measuredat a heating temperature (T), loading (P), and heating time of period(t) based on a method described in JIS K7210. Herein, T is a temperaturehigher than a 5° C.-higher temperature than a melting point of thecomposition (R) and, it is a minimum temperature of experimentaltemperatures described in Table 1 of the JIS K7210, and P is a valueselected as ranging in 1-30 g/10 minutes in the MI value. The MI(T, P,t+10) is a value in which the heating time of period is t+10 minutes inconditions of the T and P.

The present invention No. 20 relates to a method for the preparation ofa polyester block copolymer composition (R) characterized in that thereis thermally-treated a polyester block copolymer composition (Q) inwhich 100 parts by weight of a polyester block copolymer (P) isthermally mixed with 0.1-5 parts by weight of an epoxy compound (C)having at least one epoxy groups under an inert gas atmosphere and atnot less than 120° C. in a solid phase and a temperature less than amelting point of the obtained polyester block copolymer composition (R).

The present invention No. 21 relates to a polyester block copolymercomposition which comprises thermally-mixing 100 parts by weight of apolyester block copolymer (P1) obtained by a reaction of a crystallinearomatic polyester (A1) and lactones (B) with 0.5-5.0 parts by weight ofa mono or morefunctional epoxy compound (C) and 0.01-3.0 parts by weightof a complex-formable agent for a metal (G).

The present invention No. 22 relates to a polyester block copolymercomposition as described in the present invention No. 21, characterizedin that the crystalline aromatic polyester (A1) is a polyester of anaromatic dicarboxylic acid which is an essential acid component (a) andan aliphatic dicarboxylic acid and/or a cycloaliphatic dicarboxylic acidwhich are optionally added with an aliphatic diol, an aromatic diol,and/or a cycloaliphatic diol which are a diol component (b).

The present invention No. 23 relates to a polyester block copolymercomposition as described in the present invention No. 21, in which thecrystalline aromatic polyester (A1) contains not less than 50% by weightof total of butylene terephthalate and ethylene terephthalate units.

The present invention No. 24 relates to a polyester block copolymercomposition as described in any one of the present invention Nos. 21-23,in which a copolymerization proportion (A1/B) of the crystallinearomatic polyester (A1) with the lactones (B) is 97/3-50/50 by weight.

The present invention No. 25 relates to a polyester block copolymercomposition as described in any one of the present invention Nos. 21-24,in which the epoxy compound (C) is a glycidyl type epoxy compound, acompound shown by any one of general formulae (I)-(V) described below,and a mixture thereof.

(in the formulae, R1, R2, R3 are an alkyl group and, at least one ofthose are a methyl group, and total thereof is 8 pieces. Further, “n” is0-5.) The present invention No. 26 relates to a polyester blockcopolymer composition as described in any one of the present inventionNos. 21-25, in which the complex-formable agent for a metal (G) is atleast one kind selected from the group consisting of an oxalic acidderivative, a salicylic acid derivative, and a hydrazide derivative.

The present invention No.27 relates to a heat-sensitive body for aheater cable composed of a polyester block copolymer composition asdescribed in any one of the present invention Nos. 21-26.

The present invention No. 28 relates to a polyester block copolymercomposition which comprises, in obtaining the polyester block copolymercomposition by allowing to react the crystalline aromatic polyester (A1)with the lactones (B), adding and thermally-kneading 0.5-5.0 parts byweight of an epoxy compound (C) having one or more pieces of epoxygroups (including at least 0.2 part by weight of two or more functionalepoxy compound) and 0-2.0 parts by weight of a carbodiimide compound (E)to 100 parts by weight of a polyester block copolymer (P3) obtained byallowing to react 0.1-100% by mol at least three pieces of at least onekind of a multifunctional compound (D) having at least three pieces ofcarboxylic group (i), hydroxyl group (ii), and/or an ester-formablegroup therefrom (iii) with 100% by mol of a crystalline aromaticpolyester (A1).

The present invention No. 29 relates to a polyester block copolymercomposition which comprises, in obtaining the polyester block copolymercomposition by allowing to react the crystalline aromatic polyester (A1)with the lactones (B), adding and thermally-kneading 0.1-5.0 parts byweight of at least one kind of an epoxy compound (C) having one or morepieces of epoxy groups and 0-2.0 parts by weight of a carbodiimidecompound (E) to 100 parts by weight of a polyester block copolymer (P3)obtained by allowing to react 0.1-200% by mol of at least one of amultifunctional compound (D) having at least three pieces of carboxylicgroup (i), hydroxyl group (ii), and/or an ester-formable group therefrom(iii) with 100% by mol of a crystalline aromatic polyester (A1).

The present invention No. 30 relates to a polyester block copolymercomposition as described in the present invention No. 28 or 29, in whichthe crystalline aromatic polyester (A1) is a polyester of an aromaticdicarboxylic acid which is an essential acid component (a) and analiphatic dicarboxylic acid and/or a cycloaliphatic dicarboxylic acidwhich are optionally added with an aliphatic diol, an aromatic diol,and/or a cycloaliphatic diol which are a diol component (b).

The present invention No. 31 relates to a a polyester block copolymercomposition as described in any one of the present invention Nos. 28-30,in which the crystalline aromatic polyester (A1) contains not less than50% by weight of total of butylene terephthalate and/or ethyleneterephthalate units.

The present invention No. 32 relates to a polyester block copolymercomposition as described in any one of the present invention Nos. 28-30,in which a copolymerization proportion of the crystalline aromaticpolyester (A1) with the lactones (B) is the same proportion as describedin the present invention No. 24.

The present invention No. 33 relates to a polyester block copolymercomposition as described in any one of the present invention Nos. 29-32,in which at least one kind of the multifunctional compound (D) containscarboxylic group (i) or an ester-formable group therefrom.

The present invention No. 34 relates to a polyester block copolymercomposition as described in any one of the present invention Nos. 28-33,in which the epoxy compound (C) is the same compound as described in thepresent invention No. 25.

The present invention No. 35 relates to a polyester block copolymercomposition as described in any one of the present invention Nos. 28-34,which is employed for blow molding.

The present invention No. 36 relates to a polyester block copolymercomposition (R) which comprises, in obtaining the polyester blockcopolymer composition by allowing to react the crystalline aromaticpolyester (A1) with the lactones (B), heating a polyester blockcopolymer composition (Q) in a solid phase, and the composition (Q) isobtained by formulating and melt-mixing 0.1-5.0 parts by weight of anepoxy compound (C) having one or more pieces of epoxy groups with 100parts by weight of a polyester block copolymer (P) obtained by allowingto react 0.1-200% by mol of at least one kind of a multifunctionalcompound (D) having at least three pieces of carboxylic group (i),hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with100% by mol of a crystalline aromatic polyester (A).

The present invention No. 37 relates to a polyester block copolymercomposition (R) as described in the present invention No. 36, in whichthe multifunctional compound (D) contains at least one of carboxylicgroup (i) or an ester-formable group therefrom.

The present invention No. 38 relates to a polyester block copolymercomposition (R) as described in the present invention No. 36 or 37, inwhich the epoxy compound (C) contains at least one kind of abifunctional epoxy compound.

The present invention No. 39 relates to a polyester block copolymercomposition (R) as described in any one of the present invention Nos.36-38, in which the polyester block copolymer composition (R) has anacid value of not more than 0.5 mgKOH/g and, moreover, a melting pointTm(R) is not more than a temperature of 5° C.-lower than a melting pointTm(P) of the polyester block copolymer (P) before adding the epoxycompound, that is, Tm(R)≧Tm(P)−5° C.

The present invention No. 40 relates to a polyester block copolymercomposition as described in any one of the present invention Nos. 36-39,in which a melt viscosity stability (MI−B)/(MI−A) is 0.5-2.0 which iscalculated from an MI value (MI−A) in the polyester block copolymercomposition (R) and an MI value (MI−B) after heating for 10 minutes at atemperature selected so as to be a lower temperature in the temperaturedescribed in JIS K7210 which is a temperature of 5° C.-higher thanTm(R).

The present invention No. 41 relates to a polyester block copolymercomposition as described in any one of the present invention Nos. 36-40,which is a composition for blow molding.

The present invention No. 42 relates to a method for the preparation ofa polyester block copolymer composition (R) characterized in that inobtaining the polyester block copolymer composition by allowing to reactthe crystalline aromatic polyester (A) with the lactones (B), there isheated a polyester block copolymer composition (Q) in a solid phase, andthe composition (Q) is obtained by formulating and melt-mixing 0.1-5.0parts by weight of an epoxy compound (C) having one or more pieces ofepoxy groups with 100 parts by weight of a polyester block copolymer (P)obtained by allowing to react 0.1-200% by mol of at least one of amultifunctional compound (D) having at least three pieces of carboxylicgroup (i), hydroxyl group (ii), and/or an ester-formable group therefrom(iii) with 100% by mol of a crystalline aromatic polyester (A).

The present invention No. 43 relates to a method for the preparation ofa polyester block copolymer as described in the present invention No.42, in which heating is conducted in a solid phase at conditions of froma temperature lower than a melting point in a solid phase of thepolyester block copolymer composition (R) to a temperature higher than aglass transition temperature under an inert gas atmosphere and,moreover, heating is conducted at a temperature (Ta) higher than 120° C.

Tg<Ta<Tm(R),

and

120° C.<Ta

The present invention No. 44 relates to a method for the preparation ofa polyester block copolymer as described in the present invention No.42, in which the temperature heating in a solid phase is 100- to 5° C.-lower than a melting point in a solid phase of the polyester blockcopolymer composition (R) and, moreover, heating is conducted at atemperature (Ta) higher than 150° C.

Tm(R)−100° C.≦Ta≦Tm(R)−5° C.,

and

150° C.≦Ta

The present invention No. 45 relates to a method for the preparation ofa polyester block copolymer as described in any one of the presentinvention Nos. 42-44, in which heating is conducted in a solid phase atconditions of,

(1) a temperature ranges from a temperature lower than a melting pointof the polymer to a temperature higher than a glass transitiontemperature in a solid phase and, moreover, preheating is conducted at alower temperature than 150° C. and a temperature (Tb) lower than Ta, andthen,

(2) a temperature ranges from a temperature lower than a melting pointof the polymer to a temperature higher than a glass transitiontemperature in a solid phase and, moreover, heating is conducted at atemperature higher than 120° C.,

Preheating temperature Tb

Tg<Tb<Tm(R),

Tb<150° C.,

and

Tb≦Ta

Heating temperature Ta

Tg<Ta<Tm(R),

and

120° C.<Ta

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an outlined drawing which shows an example of a structure in aheater cable.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention No. I will be illustrated in detail.

The polyester block copolymer (P1) obtained in the present invention, ifit is a copolymer having a hard segment primarily containing thecrystalline aromatic polyester (A1) and at least partially having apolylactone segment formed by a reaction of the lactones (B), is notparticularly limited and, further, in addition to an aliphatic polyetherand an aliphatic polyester, it may even contain one or more kindsselected from a polyester composed of a combination of an aromaticdicarboxylic acid, an aliphatic dicarboxylic acid, or an oxycarboxylicacid with glycols having a carbon number of 2-12, and which has a lowermelting point than that of the crystalline aromatic polyester (A1) asother copolymer segments.

<Crystalline Aromatic Polyester (A1)>

The crystalline aromatic polyester (A1) is a polyester of an aromaticdicarboxylic acid which is an essential component and, an aliphaticdicarboxylic acid and/or a cycloaliphatic dicarboxylic acid which areoptionally added as an acid component (a) with an aliphatic diol, anaromatic diol, and/or a cycloaliphatic diol, and which is a polymermainly having an ester bond, and which has hydroxyl group and/orcarboxylic group, preferably, hydroxyl group at the molecular terminals.

<Acid Component (a)>

As the acid component (a) which constructs the crystalline aromaticpolyester (A1), for example, there are specifically enumeratedterephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid,biphenyl dicarboxylic acid, etc., which are an aromatic dicarboxylicacid, and an ester thereof.

Further, as the aliphatic dicarboxylic acid which is optionally added, adicarboxylic acid having a carbon number of 2-20 is appropriate and, forexample, there are specifically enumerated succinic acid, glutaric acid,adipic acid, azelaic acid, sebasic acid, dodecanoic diacid, and a dimeracid, etc.

Further, as the cycloaliphatic dicarboxylic acid, for example,1,4-cyclohexane dicarboxylic acid, etc. is enumerated.

The dicarboxylic acids, in the case of employing as a raw material, maybe even an ester, a chloride of an acid, and an anhydride.

<Diol Component (b)>

As the diol component (b) for the crystalline aromatic polyester (A1),for example, there are specifically enumerated 1,4-butanediol,1,3-butanediol, 1,2-butanediol, ethyleneglycol, propylene glycol,1,2-propanediol, 1,3-propanediol, 1,5-pentanediol,3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,6-hexanediol, neopentylglycol, and a polymethylene glycol, etc. which are an aliphatic diol.

Further, as the aromatic diol, for example, there are enumeratedhydroquinone, resorcinol, naphthalene diol,2,2-bis(4-hydroxyphenyl)propane, an adduct of ethylene oxide andpropylene oxide, etc. to bisphenol A, for example,2,2-bis(4-hydroxyethoxyphenyl)propane,2,2-bis(4-hydroxydiethoxyphenyl)propane,2,2-bis(4-hydroxytriethoxyphenyl)propane,and2,2-bis(4-hydroxypolyethoxyphenyl)propane, etc.

Still further, as the cycloaliphatic diol, for example, there areenumerated 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol,2,2-bis(4-hydroxyethoxycyclohexyl)propane, and an adduct of ethyleneoxide and propylene oxide, etc. to hydrogenated bisphenol A, etc.

As the crystalline aromatic polyester (A1), for example, there arespecifically enumerated a polyethylene terephthalate, polybutyleneterephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, apolyethylene-2,6-naphthalate, and a polybutylene-2,6-naphthalate, etc.Further, there can be also enumerated a copolymerized polyester in whichthere are further copolymerized an aliphatic dicarboxylic acid unit suchas isophthalic acid, adipic acid, sebasic acid, and dodecanoic diacid,and p-oxybenzoic acid unit with a mixture of the polyesters and thepolyesters. Of those, polybutylene terephthalate is particularlypreferred because of an excellent crystallinity.

As the crystalline aromatic polyester (A1), there may be employed onesproduced in a melting state by publicly-known methods without anymodifications, or there may be even employed ones melted again afterhaving once molded into a solid such as pellets and, further, there maybe even employed ones melted after having added the lactones (B)described below.

<Lactones (B)>

The lactones (B), if those are a cyclic ester which can be ring-opened,are not particularly limited, and there are enumerated a variety of 4 to12-membered lactones, glycolide, lactide, and a mixture thereof, etc. Ofthose, there are preferred ε-caprolactone, δ-valerolactone,β-propiolactone, glycolide, and an alkylated product thereof, forexample, β-methyl-δ-valerolactone, and lactide, etc. Particularly,ε-caprolactone is preferred from a viewpoint of a thermal stability, areactivity with the crystalline aromatic polyester, and profitability.

As use proportion of both in a reaction of the crystalline aromaticpolyester (A1) with the lactones (B), (crystalline aromatic polyester(A1))/(lactones (B)) ranges in preferably 95/5-20/80, and morepreferably 90/10-30/70. In the case that the crystalline aromaticpolyester (A1) exceeds the upper limit of the use proportion, physicalproperties as a noncrystallinity or low crystallinity resin areinsufficient in a polyester block copolymer (P1) obtained and,contrarily, in the case that it is less than the lower limit of the useproportion, flexibility is unpreferably insufficient as an elastomerresin.

In the present invention No. I, (B+0. 5)% by weight of lactones (B) areintroduced into A% by weight of a crystalline aromatic polyester (A1)and, B% by weight of lactones (B) is allowed to react with A% by weightof a crystalline aromatic polyester (A1) to obtain 100% (herein,A+B=100) by weight of the polyester block copolymer (P1), whereby, notlass than 0.5% by weight of unreacted lactones (B) are remained in 100%by weight of the copolymer (P1) after having prepared the polyesterblock copolymer (P1).

The above value of not less than 0.5% by weight is an amount of theunreacted lactones (B) which still remain in a period at which therecompletely terminates a reaction of A% by weight of the crystallinearomatic polyester (A1) with B% by weight of the lactones (B) which areraw materials, and it is a value selected as a basic value of (A+B=100)%by weight. In a higher value exceeding 0.5% by weight, reaction ratebecomes quick. In the case of less than 0.5% by weight, reaction ratebecomes remarkably low, resulting in that practicability is lost.

It is to be noted that the above-described unreacted lactones are aportion of the lactones employed in the reaction, and those remain afterthe reaction and, those mean the lactones having a same chemicalstructure as that of the lactones employed.

Usually, although cyclic esters are thermally produced again after oncehaving reacted, or form a dimer and a trimer having a reactivity, thosehave a same structure as that in the raw materials, and the unreactedlactones do not include the dimer and the trimer. Reaction massincluding the polyester block copolymer (P1) obtained in the reaction isanalyzed by a variety of methods (there is enumerated a gaschromatographic analysis described hereinafter), and residual componentsactually observed are the unreacted lactones.

In the present invention No. I, the polyester block copolymer (P1), asdescribed hereinabove, contains the hard segment based on thecrystalline aromatic polyester (A1) and the segment based on thelactones (B), and it may further contain even other copolymer segments.A more specific method for the preparation thereof includes acombination of the aliphatic polyether (A2); the polylactone (A3); andthe aromatic dicarboxylic acid, the aliphatic dicarboxylic acid oraliphatic oxycarboxylic acid with glycols having a carbon number of2-12, and there may be even employed a noncrystalline or low crystallinepolyester (collectively referred to as a low crystalline polyester (A4))which is prepared so as to not show an actual melting point in a stateintroduced into the block copolymer together with the crystallinearomatic polyester (A1) and the lactones (B) described hereinabove.

As the aliphatic polyether (A2), there are enumerated a polyethyleneglycol, a polytetramethylene glycol, and a polypropylene glycol, etc. Ofthose, the polytetramethylene glycol is particularly preferred becauseof an excellent stability and flexibility.

The polylactone (A3) is a polymer prepared by a ring-openingpolymerization of the lactones (B), there are specifically enumerated apolybutyrolactone, a polyvalerolactone, a polycaprolactone, apolyenantolactone, and a polycaprylolactone, etc. Of those, thepolycaprolactone is preferred from a viewpoint of stability.

The low crystalline polyester (A4) is an aliphatic polyester composed ofa combination of the aliphatic dicarboxylic acid or aliphaticoxycarboxylic acid with the glycols having a carbon number of 2-12 and,specifically, there are enumerated a polybutylene succinate, apoly-1,6-hexanediol succinate, and a poly-1,6-hexanediol adipate, etc.Of those, the poly-1,6-hexanediol adipate is preferred from a viewpointof stability.

The low crystalline polyester (A4) is a low crystalline polyester whichis prepared so as to not show an actual melting point in the blockcopolymer composed of a combination of the aromatic dicarboxylic acid,aliphatic dicarboxylic acid or aliphatic oxycarboxylic acid with theglycols having a carbon number of 2-12 and, specifically, it is apolyester synthesized by allowing to polycondense or ring-openingpolymerize the aromatic dicarboxylic acid such as terephthalic acid,isophthalic acid, and phthalic acid and an ester-formable derivativethereof, the aliphatic dicarboxylic acid having a carbon number of 2-12or an ester-formable derivative thereof, the diol having a carbon numberof 2-12 or an ester-formable derivative thereof, and the aliphaticoxycarboxylic acid with the glycols having a carbon number of 2-12 with4- to 7-membered lactones.

<Polyester Block Copolymer (P1)>

In the above-descriptions, it is essential that the amount of thelactones (B) to be introduce is not less than (B+0.5)% by weight withrespect to A% by weight of the crystalline aromatic polyester (A1), andthe amount of the unreacted lactones is not less than 0.5% by weight.Preferably, the amount of the lactones (B) to be introduce is not lessthan (B+1.0)% by weight, and the amount of the unreacted lactones is notless than 1.0% by weight and, more preferably, the amount of thelactones (B) to be introduce is not less than (B+2.5)% by weight, andthe amount of the unreacted lactones is not less than 2.5% by weight. Inthe case of being less than 0.5% by weight, a melting point lowers inthe polyester block copolymer (P1) obtained and, further, quantity ofheat to fuse decreases, particularly, a fusing peak gets abroad to aside of a lower melting point. On the other hand, in the case that theunreacted lactones exceeds 0.5, the amount is particularly limited,volatile components increase in the case that the polyester blockcopolymer (P1) is molded into pellets, resulting in that a workingcircumstance becomes worse and it becomes difficult to remove theunreacted lactones. Accordingly, it is preferred in not more than 20% byweight, and particularly not more than 10% by weight.

In the reaction of the crystalline aromatic polyester (A1) with thelactones (B), although catalysts for a reaction may be employed, thereaction may be even conducted in the absence of the catalysts.

As the catalysts, there can be employed a catalyst for esterificationreaction, a catalyst for a transesterification reaction and a catalystfor a ring-opening polymerization of lactones which are publicly-knownand, specifically, there are enumerated metals such as lithium,potassium, sodium, magnesium, calcium, barium, zinc, aluminum, titanium,cobalt, germanium, tin, antimony, cadmium, manganese, and zirconium, andorganic metal compounds thereof, oxides, organic acid salts, alcolates,and alkoxides, etc. Particularly, there are preferred the organic metalcompounds of tin, aluminum, titanium, zirconium, germanium, antimony,and cobalt, the oxides, organic acid salts, alcolates, and alkoxides,etc. It is to be noted that the catalysts may be even employed incombination of two or more kinds.

Temperature in the case that the crystalline aromatic polyester (A1) isallowed to react with the lactones (B), if it is those can react in auniformly mixed state under agitation, is not limited. In the case thatthe crystalline aromatic polyester (A1) can be dissolved in the lactones(B), those can be sufficiently agitated at a temperature being not morethan a melting point of the crystalline aromatic polyester (A1).However, in the case that it does not dissolve in the lactones (B) at atemperature being less than the melting point, since a decompositionreaction, etc. of the crystalline aromatic polyester (A1) proceed byheating depending upon the temperature, resulting in that there becomeworse physical properties in the polyester block copolymer (P1)obtained.

Accordingly, the reaction temperature preferably ranges in 20° C.-lowertemperature and 50° C.-higher temperature than a melting point of thecrystalline aromatic polyester (A1) to be employed. If it is thetemperature range, there can be manifested an effect in the presentinvention even in any temperature.

Reaction time of period in the reaction of the crystalline aromaticpolyester (A1) with the lactones (B) is not particularly limited, if itis a range of a reaction time of period during which the polyester blockcopolymer (P1) can be prepared by allowing to react both compounds andthere can be actualized a method for the preparation thereof in whichthe amount of the unreacted lactones remained in the polyester blockcopolymer (P1) after the reaction can be controlled in not less than0.5% by weight.

The reaction time of period in order actualize a method for thepreparation for satisfying conditions in relation to the presentinvention varies depending upon temperature, conditions of agitation,and catalysts, etc., and it is usually 2-300 minutes, more preferably5-120 minutes because productivity becomes worse by a long time reactionof period.

As an atmosphere in the case of allowing to react the crystallinearomatic polyester (A1) with the lactones (B), an inert gas atmosphereis basically preferred, or a compressed atmosphere not substantiallyhaving a gas phase portion is preferred. Color hue, molecular weight,and hydrolysis resistance, etc. in a resin become worse by the presenceof oxygen and moisture.

Pressure in the reaction of the crystalline aromatic polyester (A1) withthe lactones (B) widely ranges from an ordinary pressure to 200 kg/cm₂or so depending upon a shape of the reaction apparatus. In the case thata reaction system is under a compressed state, it is required to preventa leak of oxygen and moisture from outside, and it is preferred to inadvance remove gasses and moisture in the crystalline aromatic polyester(A1) with the lactones (B) by publicly-known methods. Specifically, theremoval is conducted by combination of a treatment for reducingpressure, purging of an inert gas, and drying operation. In all cases,it is more preferred in the presence of a smaller amount of oxygen andmoisture.

An apparatus for the reaction of the crystalline aromatic polyester (A1)with the lactones (B) is not particularly limited, if it is an apparatusin which there can be applied a variety of reaction conditions whichinclude a feed of raw materials and an inert gas, etc., heating,compressing, mixing and agitation, and discharge, etc.

As a reaction apparatus for batchwise, there is employed a tank-typereaction vessel equipped with agitating blades. It is required that amost appropriate shape of the agitating blades is selected by reactionconditions to be conducted and, usually, a double-helical ribbon bladeand a twisted lattice-shape blade, etc. are preferred. As a continuousreaction apparatus, there can be employed an apparatus, etc. which isexcellent in mixing, formation of free surface, and a surface-renewalproperty in spite of an extruder having one or two agitating rods or asame shape. Further, a static mixer, etc. is appropriate, and these maybe employed in combination of two or more kinds.

From the polyester block copolymer (P1) obtained by allowing to react ina variety of modes as described hereinabove, unreacted lactones can beremoved. Even though an operation for removing is conducted, theresufficiently manifests an elevation of a thermal property in thepolyester block copolymer (P1) as an effect by a method for thepreparation in relation to the present invention.

Removal of the unreacted lactones remaining in the polyester blockcopolymer (P1) can be actualized by reducing a pressure under heating orstreaming an inert gas, etc.

In the removal of the unreacted lactones remained, the heatingtemperature is not particularly limited because of being capable ofconducting at a condition of agitating the polyester block copolymer(P1) in a melted state, or even in a state molded into pellets orpowder. In the case of conducting in a melted state, there is preferreda temperature selected from a range of 5- to 50° C.-higher temperaturethan a melting point of the polyester block copolymer (P1). In the caseof exceeding 50° C., a decomposition reaction thermally proceeds, andphysical properties as a resin become worse in the polyester blockcopolymer (P1). On the other hand, in the case of conducting in a statemolded into pellets or powder, there is preferred a temperature range of5- to 100° C.-lower temperature than a melting point of the polyesterblock copolymer (P1) in consideration of avoidance of a blocking problemaccompanied by heating between pellets or powder.

Specifically, it is preferably selected within a range of 100-280° C.

In the removal of the unreacted lactones remained, a pressure in thecase of conducting under a reduced pressure is basically more preferredin a lower range, and it is preferably not more than 200 torr, and morepreferably 0.1-50 torr in consideration of profitability.

On the other hand, in the case of conducting under an inert gasatmosphere which is not under a reduced pressure, including a case ofconducting under streaming the gas, there is preferably employed atypical inert gas such as nitrogen, argon, and helium. However, in thecase of capable of maintaining the polyester block copolymer (P1) at asufficiently low temperature and in the case that a reactionthermally-deteriorated by oxygen does not become problematic, air can bealso employed. Also in the case, it is more preferred to remove moisturein a state as low as possible.

As an apparatus for removing the unreacted lactones remained, if it isan apparatus by which the unreacted lactones can be taken out of asystem in a volatile state, it is not particularly limited.

For example, a batchwise tank-type reaction vessel may be even maintainin a reduced pressure state, and there may be continuously or batchwiseemployed an apparatus having one or more agitating rods for agitation,surface renewal, and surface formation in a horizontal or verticalcolumn-type reaction vessel. Further, two or more sets of theapparatuses may be employed in combination. In a solid state, there canbe also employed either a column-type apparatus such as a hopper dryer,or an apparatus in which a tank-type reaction vessel can be vibrated orrotated.

Conditions such as the above-described reaction, temperature, pressure,agitation in relation to the removal of the unreacted lactones may beoptionally appropriately modified without being maintained untiltermination of an actual synthesis of the polyester block copolymer (P1)or termination of the removal of the unreacted lactones.

In the case of a method for the preparation in which a batchwiseapparatus is employed, since resins are gradually taken out, and theunreacted lactones are occasionally removed, although an amount of theunreacted lactones fluctuates in every taking out, the amount of theabove-described unreacted lactones remained is a weighted mean value inan amount of unreacted lactones in every resins taken out. On the otherhand, in the case that a removal operation of the unreacted lactones isconducted in an identical apparatus from a total reaction mass withoutgradually taking out resins after a reaction in which a batchwiseapparatus is employed, the amount is shown by an amount of the unreactedlactones immediately before conducting a removal operation.

In the case that the crystalline aromatic polyester is allowed to reactwith the lactones in a continuous reaction apparatus, the amount showsan amount of the unreacted lactones in resins continuously taken out.After that, there is conducted a removal operation of the unreactedlactones.

An effect by the present invention becomes higher in the case that atleast partial step, particularly, a polymerization step is continuouslyconducted. This depends upon that it is easy to constantly maintain theamount of the unreacted lactones in relation to the present invention inthe continuous polymerization process.

In the present invention, the reaction of the crystalline aromaticpolyester (A1) with the lactones (B) may be even conducted under thepresence of an antioxidant and a thermal stabilizer, etc.

Such the compounds may be added at any one of an initial period of thereaction, during the reaction, and a final period of the reaction.Further, there may be simultaneously or separately added additives suchas pigments, a weatherability agent, a metal-capping agent, fillers, anda modifier together with the above-described additives.

The polyester block copolymer (P1) obtained by the present invention No.I can be employed in every uses such as parts for cars, parts forelectric equipments, and industrial goods which are molded by moldingmethods such as injection molding, extrusion moding, and blow molding,etc. and, particularly, it is preferably employed for uses such as afusibly-cutting layer in a heater cable in which properties in meltingare important.

Hereinafter, the present invention No. II will be illustrated in detail.

As described hereinabove, there may be highly-polymerized a reactionmass of the polyester copolymer (P1) obtained by the reaction of thecrystalline aromatic polyester (A1) with the lactones (B) in the presentinvention No. I in which a fixed amount of the unreacted lactones areremained by a polycondensation of the the polyester block copolymer (P)in a solid phase while removing the unreacted lactones, or the reactionmass may be even highly-polymerized by a polycondensation whilebalancing the reaction of the polyester copolymer with the unreactedlactones in a solid phase without removing the unreacted lactones.

In the case of removing the unreacted lactones remained the reactionmass of the polyester block copolymer (P1), there can be applied themethod for removing the unreacted lactones, apparatus, and conditionsdescribed in the present invention No. I.

In the second step, reaction in the solid phase is conducted at atemperature not more than a melting point of a polyester block copolymerhaving a high molecular weight (P′1) obtained, and it is preferablyconducted at not more than 5° C.-lower temperature than a melting pointof the polyester block copolymer (P′1) and not less than 130° C. for thepurpose of allowing to proceed a polycondensation reaction whileavoiding a problem such as blocking, and more preferably at not morethan 20° C.-lower temperature than the melting point and not less than150° C.

In the polycondensation in a solid phase, an atmosphere may be any oneof under a reduced pressure or streaming a gas and, as the gas, thereare preferred inert gases such as nitrogen, argon, and helium.

In the case that the gas pressure in the atmosphere is in a reducedpressure, it is more preferred in as lower pressure as possible, and itpreferably ranges in not more than 200 torr, and more preferably 0.01-50torr.

Since moisture and oxygen in the inert gases make physical properties ofresins worse, a smaller amount is more preferred, and those can beremoved by publicly-known means. Reaction time of period in a solidphase can be freely selected by physical properties of resins obtained,and it usually ranges in 1-50 hours, preferably 6-35 hours, and morepreferably 10-24 hours.

As an apparatus for allowing to react in a solid phase, if it is anapparatus by which the above-described operation can be conducted, it isnot particularly limited. For example, there can be also employed eithera column-type apparatus such as a hopper dryer, or an apparatus in whicha tank-type reaction vessel can be vibrated or rotated. A more preferredoperation can be conducted by separately arranging an apparatus forremoving moisture and alcoholic components such as glycols produced byheating and residual volatile components such as unreacted lactonescontained in the resins.

In the case of continuously conducting partial steps, particularly, astep for obtaining the polyester block copolymer (P′1) and a succeedingsolid-phase reaction step, an effect by the present invention No. IIbecomes higher. This depends upon that it becomes easy to constantlymaintain the amount of the unreacted lactones contained in the polyesterblock copolymer (P′1) in the continuous steps.

In the present invention, from the polyester block copolymer having ahigh molecular weight obtained by allowing to react as describedhereinabove, unreacted lactones can be also removed. Even though such anoperation is conducted, there sufficiently manifests an effect forelevating a thermal property in the polyester block copolymer having ahigh molecular weight by a method for the preparation in relation to thepresent invention. It is to be noted that since the amount of theunreacted lactones remained in the polyester block copolymer beforebeing moved to the solid-phase reaction step has influence upon physicalproperties of the polyester block copolymer having a high molecularweight obtained, a preferred polyester block copolymer is obtained by inadvance adding a fixed amount of lactones with respect to thecrystalline polyester (A), and there can be adjusted a proportion ofunits based on the crystalline polyester (A) with respect to units basedon the lactones (B) in the copolymer.

As a method, etc. for removing the unreacted lactones from a reactionproduct of the polyester block copolymer having a high molecular weight(P′1), there can be applied a variety of methods, apparatuses, andconditions employed for removing the unreacted lactones from thepolyester block copolymer (P1) prepared in the first step of the presentinvention No. I, and the method, etc. may be different from the methodsemployed for removing the unreacted lactones from the polyester blockcopolymer (P1).

The above reaction and conditions for removing the unreacted lactonescan be adjusted by changing temperatures, pressures, and agitatingconditions, etc. until the polyester block copolymer having a highmolecular weight (P′1) is actually obtained and the removal of theunreacted lactones terminates.

The polyester block copolymer having a high molecular weight (P′1)obtained by the present invention No. II can be employed in every usessuch as parts for cars, parts for electric equipments, and industrialgoods which are molded by molding methods such as injection molding,extrusion molding, and blow molding, etc. and, particularly, it ispreferably employed for uses such as a fusibly-cutting layer in a heatercable in which properties in melting are important.

Hereinafter, the present invention No. III will be illustrated indetail.

In the polyester block copolymer (P) to be employed in the presentinvention No. III, a method for the preparation thereof is notparticularly limited, if it is a polyester block copolymer containing ahard segment which is a crystalline aromatic polyester and a softsegment which is a copolymer component composed of an aliphaticpolyether; a polylactone; and an aliphatic polyester, or a copolymercomponent composed of a combination of an aromatic dicarboxylic acid, analiphatic dicarboxylic acid, and an aliphatic oxycarboxylic acid withglycols having a carbon number of 2-12, and the copolymer component iscombined by at least one or more kinds selected from polyesters having alower melting point than that of the crystalline aromatic polyesterwhich constructs the hard segment.

One of the polyester block copolymer (P) is a polyester block copolymer(P1) which is obtained by a reaction of the crystalline aromaticpolyester (A1) with the lactones (B). As the copolymer (P1), there canbe also employed the polyester block copolymer (P1) or the polyesterblock copolymer having a high molecular weight (P′1) shown in thepresent inventions No. I and No. II.

Another one of the polyester block copolymer (P) may be a polyesterblock copolymer (P2) which is obtained by a condensation and/orring-opening polymerization of monomer components which construct thecrystalline aromatic polyester (A1), monomer components which constructa low crystalline polyester (A4); an aliphatic polyether (A2); and/or apolylactone (A3).

As a method for the preparation of the polyester block copolymer (P),for example, there may be a method by a polycondensation of adicarxoxylic acid component or an ester-formable derivative with a diolcomponent, or an ester-formable derivative under the presence of apolymer constructing the soft segment in advance prepared or, even amethod by a polycondensation or a ring-opening polymerization of adicarxoxylic acid and an ester-formable derivative which construct asoft segment, a diol, or an ester-formable derivative, and/or lactonesunder the presence of a polymer constructing the hard segment.

The above-described methods can be batchwise or continuously conductedand, moreover, the polyester block copolymer (P) can be obtained by atank-type reaction vessel equipped with agitating blades, a column-typereaction vessel equipped with agitating blades, a column-type reactionvessel equipped with fixed agitating blades, and even by an extruder.

<Hard Segment>

<Crystalline Aromatic Polyester>

As the crystalline aromatic polyester (A1) which constructs a hardsegment in the present invention, there can be employed the same ones asillustrated in the present invention No. I.

<Soft Segment>

In the present invention, an aliphatic polyether (A2), a polylactone(A3), and a low crystalline polyester (A4) construct a soft segment.There can be employed the same ones as illustrated in the presentinvention No. I.

The above-described respective components which construct the softsegment have a lower melting point than that of the crystalline aromaticpolyester which constructs a hard segment and, in almost cases, it doesnot show crystallinity in the polyester block copolymer (P). In the casethat the soft segment is an aliphatic polyester component, a treatmentin a melting state ends to proceed a transesterification reaction inaddition to a decomposition reaction by heating, and it unpreferablylowers a melting point in a block copolymer composition (R). In thepresent invention No. III, since a heating treatment is conducted at alower temperature, there can be remarkably reduced decomposition,discoloration, and a decline of a melting point.

As a proportion of the hard segment component with respect to the softsegment ranges in preferably 99/1-20/80, and more preferably 98/2-30/70by weight, the hard segment component is composed of the crystallinearomatic polyester in the polyester block copolymer (P) to be employedin the present invention No. III, and the soft segment is composed of apolyether or aliphatic polyester having a lower melting point than that,(crystalline aromatic polyester)/(constructing components of the softsegment)

It is to be noted that the hard segment and the soft segment are notalways chemically bonded, and a portion of those may form also amixture.

In the case that a polycondensation reaction or a ring-openingpolymerization are conducted in order to obtain the polyester blockcopolymer (P), catalysts may be even added and, reactions may be evenconducted under the absence of catalysts. As the catalysts, there can beemployed same ones as described in the present invention No. I.

<Epoxy Compound (C)>

The epoxy compound (C), which is allowed to react with the polyesterblock copolymer (P) in the present invention No. III, has at least oneepoxy group, and it is not particularly limited in a structure thereof.

As the epoxy compound (C), there can be employed an epoxy compound (C1)having one epoxy group and an epoxy compound (C2) having at least twoepoxy groups, and both compounds can be employed in combination. Forexample, there are enumerated a bisphenol type epoxy compound obtainedby a reaction of bisphenol A with epichlorohydrin, a novolak type epoxycompound obtained by a reaction of a novolak resin with epichlorohydrin,glycidyl esters obtained by a reaction of a carboxylic acid withepichlorohydrin, a cycloaliphatic compound-type epoxy compound obtainedfrom a cycloaliphatic compound, glycidyl ethers obtained from anaromatic compound and epichlorohydrin, an epoxidized butadiene, and anepoxy compound obtained from a compound having a double bond and aperoxide.

Specifically, there are enumerated an epoxy compound (C1) having oneepoxy group such as methyl glycidylether and phenyl glycidylether, andan epoxy compound (C2) having at least two epoxy groups such asdiethylene glycol diglycidylether, diglycidyl phthalate, diglycidylterephthalate, diglycidyl hexahydrophthalate,3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, an epoxidizedpolybutadiene, and an epoxidized styrene-butadiene-styrene blockcopolymer (an epoxidized SBS).

In the present invention No. III, addition amount of the epoxy compound(C) depends upon the amount of hydroxyl groups or carboxylic groupswhich exist in terminals of the polyester block copolymer (P) orproperties to be required in a composition to be finally obtained, andit is preferably 0.1-5 parts by weight, and more preferably 0.2-3 partsby weight based on 100 parts by weight of the polyester block copolymer(P). In the case that the addition amount of the epoxy compound (C) isless than 0.1 part by weight, an action and effect (particularly, aneffect for elevating heat resistance and hydrolysis resistance) by thepresent invention is not significantly shown and, in a large amount suchas exceeding 5 parts by weight, it adversely affects to surface flatnessand mechanical properties in a molded article.

The polyester block copolymer (P) is mixed with the epoxy compound (C)in a melted state. A method for mixing thereof is not limited at alland, if it is a method which is capable of uniformly mixing, any methodscan be applied. Temperature of the epoxy compound (C) in melt-mixingranges in preferably 3° C.- to 60° C.-higher temperature, and morepreferably 5° C.- to 40° C.-higher temperature than a melting point ofthe polyester block copolymer (P). In the case that the temperature inmelt-mixing is higher, decomposition reaction is thermally accelerated,whereby, resulting in that heat resistance, hydrolysis resistance, andcolor hue become worse. In the case that the temperature in melt-mixingis lower, there become worse crystallization and dispersion conditionsof the epoxy compound (C). Time of period in melt-mixing is 10 second to10 minutes or so, preferably, it is set up in 30 second to 5 minutes.

The reaction of the polyester block copolymer (P) with the epoxycompound (C) can be conducted under the presence of catalysts. There canbe employed all catalysts which can be usually employed in a reaction ofepoxides and, as specific examples, there are enumerated amines,phosphorus compounds such as triphenyl phosphine (TPP), a carboxylicacid, an organic sulphonic acid, sulphuric acid, and an acidic compoundthereof, for example, a metal salts such as alkali metals and alkaliearth metals. Further, the catalysts may be employed in combination oftwo or more kinds.

The catalysts may be simultaneously added together with the epoxycompound (C) and, may be added after dispersing the epoxy compound (C)into the polyester block copolymer (P) in a melted state or, contrarily,the epoxy compound (C) may be even added after dispersing the catalystsinto the polyester block copolymer (P).

In the present invention No. III, an effect by the present invention canbe effectively actualized by mixing one or more kinds of compoundsselected from the group consisting of a hindered phenol-based compound,a sulphur-based compound, a phosphorus-based compound, an amine-basedcompound, and a hindered amine-based compound as a stabilizer.

Since the stabilizers have an effect for preventing oxidation to thepolyester block copolymer composition or giving a thermal stabilitythereto, those are usually added to the polyester block copolymer (P)which is employed a raw material.

As specific examples of the stabilizers, there are enumerated analkylated monophenol, for example, 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexcylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol,2,4-dimethyl-6-(1′-methyl-undec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadecyl-1′-yl)phenol,2,4-dimethyl-6-(1′-methyl-tridec-1′-yl)phenol, and a mixture thereof,alkylthiomethylphenol, for example,2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-didodecylthiomethyl-4-nonylphenol, hydroquinone and an alkylatedhydroquinone, for example, 2,6-di-tert-butyl-4-methoxyphenol,2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone,2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyphenyl stearate, andbis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate; a cumarone derivative,for example, α-tocopherol. β-tocopherol, γ-tocopherol, δ-tocopherol, anda mixture thereof (vitamin E); a hydroxylated thiodiphenylether, forexample, 2,2′-thiobis(6-tert-butyl-4-methylphenol),2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thio-bis(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl)disulphide; an alkylidenebisphenol, for example, 2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-(α-methylcyclohexylphenol,2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylidenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylidenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylidenebis(2,6-di-tert-butylphenol),4,4′-methylidenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethyleneglycol=bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butylate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methlyphenyl]terephthalate,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)-pentane, O-, N- andS-benzyl compounds, for example,3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxybenzylether,octadecyl=4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate,tridecyl=4-hydroxy-3,5-di-tert-butylbenzyl-mercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiophthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulphide,isooctyl=3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate;hydroxybenzylmaloate, for example,2,2-bis(3,5-di-tert-butyl-4-hydroxy-5-methylbenzyl)dioctadecyl maloate,2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)di-dodecylmercaptoethyl=maloate,2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)maloate=bis[4-(1,1,3,3-tetramethylbutyl)-phenyl];a hydroxybenzyl aromatic compound, for example,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; a triazinecompound, for example,2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate; abenzylphosphonate, for example,2,5-di-tert-butyl-4-hydroxybenzyldimethylphosphonate,3,5-di-tert-butyl-4-hydroxybenzyldiethylphosphonate,3,5-di-tert-butyl-4-hydroxybenzyldioctadecylphosphonate,3,5-di-tert-butyl-4-hydroxy-3-methylbenzyldioctadecylphosphonate,calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylmonoethylphosphonate;an acylaminophenol, for example, lauric 4-hydroxyanilide, stearic4-hydroxyanilide, octyl=N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate;an ester of the following mono or polyvalent alcohol withβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, an example of thealcohol: methanol, ethanol, n-octanol, isooctanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethyleneglycol, 1,2-propanediol,neopentylglycol, thiodiethyleneglycol, diethyleneglycol,triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)succinic diamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane; an ester ofthe following mono or polyvalent alcohol withβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionate, an example of thealcohol: methanol, ethanol, n-octanol, isooctanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethyleneglycol, 1,2-propanediol,neopentylglycol, thiodiethyleneglycol, diethyleneglycol,triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)succinic diamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane; an ester ofthe following mono or polyvalent alcohol withβ-(3,5-dicyclohexyl-4-hydroxyphenyl)propionate, an example of thealcohol: methanol, ethanol, n-octanol, isooctanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethyleneglycol, 1,2-propanediol,neopentylglycol, thiodiethyleneglycol, diethyleneglycol,triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)succinic diamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane; an ester ofthe following mono or polyvalent alcohol withβ-3,5-di-tert-butyl-4-hydroxyphenyl)acetate, an example of the alcohol:methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol,1,9-nonanediol, ethyleneglycol, 1,2-propanediol, neopentylglycol,thiodiethyleneglycol, diethyleneglycol, triethyleneglycol,pentaerythritol, tris(hydroxyethyl)isocyanurate,N,N′-bis(hydroxyethyl)succinic diamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane;β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic amide, for example,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylene diamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine; anamine-based antioxidant, for example,N,N′-diisopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(naphtyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulphamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphtylamine, N-(4-tert-octylphenyl)-1-naphtylamine,N-phenyl-2-naphtylamine, octylated diphenylamine, for example,p,p′-di-tertiary-butyloctyl diphenylamine, 4-n-butylaminophenol,4-butylylaminophenol, 4-nonanoyl aminophenol, 4-dodecanoylaminophenol,4-octadodecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-d-tertiarybutyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)aminoethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tertiary-octylated N-phenyl-1-naphtylamine, a mixture of a mono- anddialkylated tert-butyl/tert-octyldiphenylamine, a mixture of a mono- anddialkylated tert-butyl/tert-nonyldiphenylamine, a mixture of a mono- anddialkylated tert-butyl/tert-dodecyldiphenylamine, a mixture of a mono-and dialkylated isopropyl/isohexcyldiphenylamine, a mixture of a mono-and dialkylated tert-butyldiphenylamine,2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiadine, phenothiadine, a mixtureof a mono- and dialkylated tert-butyl/tert-octylphenothiadine, a mixtureof a mono- and dialkylated tert-butyloctylphenothiadine,N-allylphenothiadine, N,N,N′,N′-tetrapheyl-1,4-diaminobuto-2-en,N,N-bis(2,2,6,6-tetramethyl-pyperido-4yl)hexamethylenediamine,bis(2,2,6,6-tetramethylpyperido-4yl)sebacate,2,2,6,6-tetramethyl-pyperidine-4-ol; 2-(2′-hydroxyphenyl)benzotriazole,for example, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methyl-phenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octylcarbonylethyl)phenyl)-5-chloro-benzotriazole,and a mixture thereof,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenyl)benzotriazole,and2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-yl-phenol];an esterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethyleneglycol 300; [R—CH₂CH₂—COO(CH₂)₃—]₂ (in the formula,R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazole-2-yl-phenyl);2-hydroxybenzophenone, for example, 4-hydroxy-, 4-methoxy-, 4-octyloxy-,4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2,4-trihydroxy-, and2′-hydroxy-4,4′-dimethoxy-derivatives; a substituted and nonsubstitutedester of benzoic acid, for example, 4-tert-butylphenyl salicylate,phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol,bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol,3,5-di-tert-butyl-4-hydroxy benzoicacid2,4-di-tert-butylphenyl,3,5-di-tert-butyl-4-hydroxy benzoic acid hexadecyl,3,5-di-tert-butyl-4-hydroxy benzoic acid2-methyl-4,6-di-tert-butylphenyl; a hindered amine, for example,bis(2,2,6,6-tetramethyl-4-pyperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-pyperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-pyperidyl)sebacate,n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmaloate=bis(1,2,2,6,6-pentamethyl-4-pyperidyl), a condensation productof 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypyperidine withsuccinic acid, a condensation productof1-N,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediamine with4-tert-octyl-amino-2,6-dichloro-1,3,5-triazine,nitrylotriacetictris(2,2,6,6-tetramethyl-4-pyperidyl),1,2,3,4-butanetetracarboxylic acidtetrakis(2,2,6,6-tetramethyl-4-pyperidyl),1,1′-(1,2-ethanedyl)-bis(3,3,5,5-tetramethylpyperadinone)4-benzoyl-2,2,6,6-tetramethylpyperidine,4-stearyloxy-2,2,6,6-tetramethylpyperidine,2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonic acidbis(1,2,2,6,6-pentamethylpyperidyl),3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspyro[4,5]decane-2,4-dion,bis(1-octyoxy-2,2,6,6-tetramethylpyperidyl)sebacate,bis(1-octyoxy-2,2,6,6-tetramethylpyperidyl)succinate, a condensationproduct of N,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediaminewith 4-morpholino-2,6-dichloro-1,3,5-triazine, a condensation product of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethyl-4-pyperidyl)-1,3,5-triazinewith 1,2-bis(3-aminopropylamino)ethane, a condensation product of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentmethyl-4-pyperidyl)-1,3,5-triazinewithl,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspyro[4,5]decane-2,4-dion,3-dodecyl-1-(2,2,6,6-tetramethyl-4-pyperidyl)pyrodine-2,5-dion,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-pyperidyl)pyrodine-2,5-dion, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpyperidines, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediamine with4-cyclohexylamino-2,6-di-chloro-1,3,5-triazine, a condensation productof 1,2-bis(3-aminopropylamino)ethane with2,4,6-trichloro-1,3,5-triazine, and4-butylamino-2,2,6,6-tetramethyl-4-pyperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-pyperidyl)-n-dodecylsucsineimide, N-(1,2,2,6,6-pentmethyl-4-pyperidyl)-n-dodecylsucsineimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spyro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxo-spyro[4,5]decanewith epichlorohydrin; 2-(2-hydroxyphenyl)-1,3,5-triazine, for example,2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-3-octloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl)-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine; aphosphite or a phosphonite, for example, triphenyl phosphonite, diphenylphosphonite=alkyl, phenylphosphonite=dialkyl, trisnonylphenylphosphonite, lauryl phosphonite, trioctadecyl phosphonite,distearyl=pentaerythritol=diphosphite,tris(2,4-di-tert-butyl-phenyl)phosphonite,diisodecyl=pentaerythritol=diphosphite,bis(2,4-di-tert-butyl-4-methylphenyl )=pentaerythritol=diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)=pentaerythritol=diphosphite,bis-isodecyl=pentaerythritol=diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)=pentaerythritol=diphosphite,bis(2,4,6-tri-tert-butyl-6-methylphenyl)=pentaerythritol=diphosphite,tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenephosphite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocine,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocine,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, andbis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. Of those,tris(2,4-di-tert-butylphenyl)phosphite is preferred. Particularly,tris(2,4-di-tert-butylphenyl)phosphite is preferred.

Such the compounds may be in advance contained in the polyester blockcopolymer (P), and it may be even simultaneously added together with theepoxy compound (C) or, the epoxy compound (C) may be added afterdispersing it in the polyester block copolymer (P) in a melting stateor, contrarily, the compounds may be even dispersed in the epoxycompound (C).

Further, there may be simultaneously or separately added additives suchas pigments, a weatherability agent and a metal-capping agent, fillers,and a modifier in the case of mixing.

The polyester block copolymer composition (Q) melt-mixed as describedhereinabove becomes a polyester block copolymer composition (R) byfurther thermally-treating in a solid phase.

Temperature for thermally-treating the polyester block copolymercomposition (Q) is not less than 120° C. and, moreover, a temperatureless than a melting point of the polyester block copolymer composition(Q) obtained by thermally-treating.

In the case that the temperature for thermally-treating is not less thana melting point of the composition (R), a trouble by melting resins iscaused in handling, and a thermal decomposition reaction is furtheraccelerated. Further, in the case that the temperature forthermally-treating is less 120° C., there cannot be almost obtained aneffect of heat resistance and hydrolysis resistance by the presentinvention. More preferably, it is thermally-treated at not less than150° C. and, moreover, at 100- to 5° C.-lower temperature than the amelting point of the composition (R).

An atmosphere for thermally-treating is selected from inert gases suchas nitrogen, helium, and argon.

A minor amount of impurities, particularly, oxygen and moisture arepreferably decreased by methods which are usually employed. Such theinert gases may be even constantly streamed through an apparatus inwhich a thermal treatment is conducted and, if a gas atmosphere in theapparatus is nearly filled by the inert gases, a treatment may be evenconducted in a sealed state of the apparatus. Further, an inside of theapparatus may be also maintained at a reduced pressure or a compressedstate in same conditions and, the pressure may be fluctuated during thethermal treatment. In the case of reducing pressure, it is required thatthere is paid attention for volatilization of the various additivesformulated in the polyester block copolymer (P) or the polyester blockcopolymer (R). Preferably, the thermal treatment is conducted whilemaintaining at from 1 torr to an ordinary pressure under a nitrogenatmosphere of not more than 1% by volume of oxygen concentration and notmore than 1% by volume of moisture concentration. Time of period for thethermal treatment is decided according to resin properties required forthe polyester block copolymer composition (R). Usually, it is preferably1-3000 minutes. In the case of a shorter time than 1 minute, an effectby the present invention is very small and a lower time of period lowersproductivity of the polyester block copolymer composition (R) of thepresent invention.

As an another embodiment for conducting the present invention, it ispreferred to preheat the polyester block copolymer composition (Q)obtained by thermally-mixing the polyester block copolymer (P) with theepoxy compound (C) at a lower temperature than the melting point of thecomposition (R) and not more than 150° C. before maintaining at theabove-described temperature for the thermal treatment. By preheating,there can be lowered a decomposition reaction of the polyester blockcopolymer composition (Q) at an initial period of the thermal treatment,resulting in that there can be remarkably shown an effect of an increaseof melt viscosity, etc. in the present invention. In the case, as otherconditions except the temperature, there are applied the same conditionsas in the above-described thermal treatment, and it is preferred thatthe apparatus is not sealed. Further, it can be also conducted at an airatmosphere. In the case that the temperature in the preheating is higherthan 150° C., the above-described effect by the preheating is small and,there is not shown a difference from the case of preheating alone. Amore preferred temperature for the preheating is not more than 120° C.

The apparatus for conducting the heat treatment and preheating, if it isan apparatus by which the polyester block copolymer composition (Q) canbe maintained at a desired time of period, a desired atmosphere, andpressure, is not particularly limited. Those can be conducted incombination of an apparatus which can be operated batchwise orcontinuously with an apparatus for supplying the inert gases, anapparatus for maintaining a reduced pressure, an apparatus for removingimpurities from a discharged gas, and an apparatus for supplying againan inert gas from which the impurities are removed. A cone-blender and ahopper-blender, etc. can be preferably employed.

The polyester block copolymer composition (R) of the present inventioncan be obtained by thermally-treating the polyester block copolymercomposition (Q) until being given a certain property.

<Acid Value>

An acid value is one of properties which are desired in the polyesterblock copolymer composition (R). The acid value is a numerical valuewhich is measured by neutralizing acidic components contained in resinsusing a basic substance such as potassium hydroxide in a state dissolvedin solvents, and it is represented by mg number (mgKOH/g) of potassiumhydroxide to be required for neutralizing 1 g of the resin. In thecomposition (R) of the present invention, the acid value is preferred innot more than 0.5 mgKOH/g, more preferably not more than 0.2 mgKOH/g,and most preferably not more than 0.1 mgKOH/g. In the case that the acidvalue is more than 0.5 mgKOH/g, hydrolysis resistance becomes worse,resulting in that an effect is small in the present invention. Accordingto the present invention, thermal decomposition and discolorationdecrease by a lower temperature for thermally-treating, and such thephysical properties can be actualized by a smaller addition amount ofthe epoxy compound (C).

Further, there can become suppressed a decline of crystallinity such asa decline of a melting point by the addition of the epoxy compound (C).

<Melt Viscosity Stability>

Further, another property desired in the polyester block copolymercomposition (R) is a melt viscosity stability. In the case that theepoxy compound (C) employed remains in a large amount in an unreactedstate, fluctuation of the viscosity is observed by remelting. The meltviscosity stability is represented by formula MI (T, P, and t+10)/MI (T,P, and t). In the formula, the melt index (MI (T, P, and t)) value is avalue measured at heating temperature (T), loading (P), and heating time(t) based on a method described in JIS K7210. Herein, T is not less than5° C.-higher temperature than the melting point of the composition (R),and it is a lowest temperature of experimental temperature described inTable 1 of the JIS K7210 and, P is a value selected so that the MI valuebecomes a range of 1-30 g/10 minutes. The MI (T, P, and t+10) value is avalue in the case that the heating temperature is t+10 minutes at theconditions of the above T and P. In the composition (R) obtained in thepresent invention III, the melt viscosity stability is 0.5-2.0, morepreferably 0.75-1.50, and most preferably nearly 1.

By the method of the present invention, since the thermal treating isconducted at a lower temperature, the remaining epoxy compound (C) canbe allowed to sufficiently react while suppressing thermal decompositionand discoloration as low as possible, resulting in that the viscosityfluctuation can be reduced in a molding process.

In the polyester block copolymer composition (R) of the presentinvention No. III prepared as described hereinabove, color hue isclearly improved compared to a conventional resin composition obtainedby melt-mixing alone. This depends upon that the treatment in a meltingstate for attaining any one of the two properties can be finished in ashort time in the present invention III.

<Melting Point>

In the polyester block copolymer composition (R) prepared by the presentinvention No. III, decline of a melting point is smaller compared tothat of a composition (R) prepared by a conventional method, that is, bymelt-mixing alone. Melting point (Tm (R)) of the composition (R) ispreferably not less than 10° C.-lower temperature than the melting point(Tm (P)) of the polyester block copolymer (P) which is a raw material.

Tm(P)−10° C.≦Tm(R)

Further, it is preferably not less than 5° C.-lower temperature than themelting point (Tm (P)) of the copolymer (P), and more preferably notless than 3° C.-lower temperature.

Accordingly, the polyester block copolymer composition (R) obtained bythe present invention No. III is more excellent in any one of heatresistance, hydrolysis resistance, color hue, an increase ofmelt-viscosity and melt-viscosity stability compared to a composition(R) obtained by a conventional method, that is, a composition (R)obtained by melt-mixing alone.

Hereinafter, the present invention No. IV will be illustrated in detail.

The present invention No. IV relates to a polyester block copolymercomposition comprising heating and kneading after formulating 0.5-5parts by weight of a one or more functional epoxy compound (C) and 0.01part by weight to 3.0 parts by weight of a complex-formable agent for ametal (G) with respect to 100 parts by weight of the polyester blockcopolymer (P1) obtained by allowing to react a crystalline aromaticpolyester (A1) with lactones (B).

First of all, there will be illustrated raw materials for employing thepolyester block copolymer (P1) in relation to the present invention No.IV.

<Crystalline Aromatic Polyester (A1)>

As the crystalline aromatic polyester (A1) to be employed in the presentinvention No. IV, there can be employed a polyester containing the samecomponents as the polyesters described in the present invention No. III.

As the crystalline aromatic polyester (A1) to be employed in the presentinvention, there is preferred a polyester having a high polymerizationdegree, a melting point of not less than 160° C., and a number averagemolecular weight of not less than 5,000.

Of constructing components in the crystalline aromatic polyester (A1),not less than 60% by weight of butylene terephthalate and/or ethyleneterephthalate units are desirably contained in consideration ofcrystallinity, heat resistance, or costs of raw materials.

<Lactones (B)>

As the lactones (B) for lactone-modifying the crystalline aromaticpolyester (A1), there can be employed the same lactones as in thepresent invention No. I.

Hereinafter, there is illustrated the polyester block copolymer (P1) inrelation to the present invention No. IV.

<Polyester Block Copolymer (P1)>

The polyester block copolymer (P1) in relation to the present inventionNo. IV is obtained by allowing to react the lactones (B) with terminalgroups in the above-described crystalline aromatic polyester (A1) by anaddition-reaction. Copolymerization ratio (A/B) of the crystallinearomatic polyester (A1) with the lactones (B) is 97/3-50/50 by weight,particularly, preferably 90/10-55/45 by weight. In the case that theratio of the lactones (B) is smaller than the range, flexibility of thepolyester block copolymer does not manifest, resulting in that it is notappropriate for a heat-sensitive body and, in the case that it is largerthan the range, heat resistance lowers in the polyester block copolymer.

Further, the crystalline aromatic polyester (A1) can be allowed to reactwith the lactones (B) through heating and kneading by optionally addinga catalyst.

Methods for allowing to react the crystalline aromatic polyester (A1)with the lactones (B), for example, are reported in detail inJP-B-73004115 and JP-B-77049037 Official Gazettes, U.S. Pat. No.2,623,031, JP-B-85004518, JP-B-91077826, and JP-B-88031491 OfficialGazettes, etc.

Hereinafter, there is illustrated the epoxy compound (C) which isallowed to react with the polyester block copolymer (P1).

<Epoxy Compound (C)>

The epoxy compound (C), if it is a compound having at least one epoxygroups in the molecule, is not particularly limited in the structure.

However, a cycloaliphatic or glycidyl ester type epoxy compound is morepreferred than a glycidyl ether type epoxy compound in consideration ofthermal history in formulating or molding a composition.

As the cycloaliphatic epoxy compound, although there can be specificallyexemplified compounds shown in general formulae (I)-(V), it is notlimited thereto.

(in the formula, R1, R2, and R3 are an alkyl group, and at least one ofthose are a methyl group, and total of carbon numbers is 8 pieces.Further, “n” is 0-5.)

As the glycidyl ester type epoxy compound other than the above-described(II) and (III)-(V), there are enumerated a mono and diglycidyl ester ofphthalic acid, a mono and diglycidyl ester of methyltetrahydro phthalicacid, a mono and diglycidyl ester of terephthalic acid, a mono, di, andtriglycidyl ester of trimellitic acids, and a mono and diglycidyl esterof a dimer acid, etc.

Further, as the cycloaliphatic epoxy compound other than theabove-described formula (I), there are enumerated Celloxide 2081 (anadduct of ε-caprolactone dimer to3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate), Celloxide2083 (an adduct of ε-caprolactone trimer), Celloxide 2085 (an adduct ofε-caprolactone tetramer), Epolead GT300 and Epolead GT400 (both aretrade name, and obtained by epoxidation of a compound obtained by anesterification of tetrahydrophthalic anhydride with tetrahydrobenzylalcohol or a lactone-modified product thereof) which are manufactured byDaicel Chemical Industries, Ltd., and bis(3,4-epoxycyclohexyl)adipate,etc.

As the glycidyl ether type ones, there are enumerated methylglycidylether, phenylglycidyl ether, a polyethylene glycol monophenylglycidylether, ethylene glycol diglycidyl ether, and ethylene glycol diglycidylether, etc.

In the present invention, there can be employed one or more kinds of theepoxy compounds.

<Complex-formable Agent for a Metal (G)>

As the complex-formable agent for a metal (G) to be formulated in thepolyester block copolymer composition of the present invention IV, thereare employed an oxalic acid derivative, a salicylic acid derivative, ahydrazide derivative, and a mixture thereof.

The complex-formable agent for a metal (G) is not particularly limited,if it is a compound which forms a metal complex compound with metal ionswhich are dissolved out of metals such as copper and a copper alloywhich are contact with the polyester block copolymer composition, and ithas a structure which is capable of preventing deterioration byoxidation.

As the oxalic acid derivative, there are enumerated oxalicbisbenzylidene hydrazide andN,N′-bis{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propyonyloxy]ethyl}oxamide,etc., and as the salicylic acid derivative, there are enumerated3-(N-salicyloyl)amino-1,2,4-triazole and decanedicarboxylic disalicyloylhydrazide, etc. As the hydrazide derivative, there are enumeratedN,N′-bis{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propyonyloxy]ethyl}hydrazineand bis(2-phenoxypropionyl)hydrazide isophthalate, etc.

<Polyester Block Copolymer Composition (Q)>

In the polyester block copolymer composition (Q) in relation to thepresent invention IV, formulating amount of the epoxy compound (C) is0.5-5.0 parts by weight, and preferably 1.0-4.0 parts by weight based on100 parts by weight of the polyester block copolymer (P1).

In the case that the formulating amount is less than 0.5 part by weight,there becomes small an effect for general heat resistance and waterresistance in the composition (Q) obtained, and a thermally-agingresistance in the composition (Q) which comes into contact with PVCremarkably lowers by hydrochloric acid removed from the PVC. Further, inthe case that the formulating amount exceeds 5.0 parts by weight,molding processability occasionally becomes worse by an influence of theunreacted epoxy compound in the composition (Q), and there is shown atendency that surface conditions becomes coarse in a molded articleprepared.

Formulating amount of the complex-formable agent for a metal (G) is0.01-3.0 parts by weight, and preferably 0.1-0.5 parts by weight basedon 100 parts by weight of the polyester block copolymer (P1).

In the case that the formulating amount is less than 0.01 part byweight, a satisfied heat resistance cannot be obtained in thecomposition (Q) which comes into contact with a metal. Further, in thecase that the formulating amount exceeds 3.0 parts by weight, it is noteconomical and, in the composition (Q) which comes into contact with ametal, dispersion possibly becomes worse, unpreferably resulting in thatheat resistance contrarily lowers.

In the polyester block copolymer composition (Q) in relation to thepresent invention IV, there can be also added the stabilizers describedin the present invention III.

Since the stabilizers have an effect for preventing oxidation or thermalstability, those are generally added to the crystalline aromaticpolyester (P1) which is usually employed as a raw material.

Further, there may be appropriately added additives such as pigments andweatherability stabilizer depending upon uses.

The composition (Q) is usually obtained by thermally kneading of theabove formulated resins. Reaction by thermally kneading is usuallyconducted by melt-kneading of resins and, in the case, catalysts may beemployed or not employed.

As the catalysts, there can be employed all catalysts which can beusually employed in a reaction of epoxy compounds. For example, therecan be employed solely or in combination of amines, phosphoruscompounds, salts of a monocarboxylic acid or a dicarboxylic acid havinga carbon number of not less than 10 with metals in the Ia and IIa groupsof elementary periodic table.

Further, temperature for thermally kneading is desirably from atemperature of 5° C.-higher than a melting point of a crystalline of thepolyester block copolymer to 280° C.

Time of period for kneading is 30 seconds to 60 minutes or so, it can beappropriately selected according to a kneading style and thetemperature.

The complex-formable agent for a metal (G), the above-stabilizer, andadditives to be formulated in the present invention IV may besimultaneously mixed together with the epoxy compound (C) and, may beindependently mixed.

The metal which comes into contact with the composition (Q) in thepresent invention is not particularly limited, if it is a metal whichcan form a metal complex compound with the complex-formable agent for ametal (G) such as a succinic acid derivative and a salicylic acidderivative, or a hydrazide derivative and can prevent a deterioratingaction by oxidation, for example, there are enumerated chromium,manganese, iron, cobalt, nickel, copper, zinc, tin, lead, and an alloywhich primarily contains thereof and, in the case of copper and a copperalloy, an effect is particularly remarkable.

The polyester block copolymer composition (Q) in relation to the presentinvention IV has an excellent heat resistance under a contact with ametal and PVC. Accordingly, it is preferred as a heat-sensitive bodywhich comes into direct contact with a short wire composed of copper anda copper alloy in a heater cable for an electric blanket and an electriccarpet or a heating wire with PVC which is a protecting layer.

Hereinafter, the present invention No. V will be illustrated in detail.

The polyester block copolymer composition (Q) of the present inventionNo. V, in the case of obtaining a polyester block copolymer compositionby allowing to react a crystalline aromatic polyester (A1) with lactones(B), is comprised adding and thermally-kneading 0.5-5.0 parts by weightof an epoxy compound (C) having one or more pieces of epoxy groups and0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts byweight of a polyester block copolymer (P3) obtained by allowing to react0.1-100% by mol of at least one of a multifunctional compound (D) havingat least three pieces of at least one kind of carboxylic group (i),hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with100% by mol of a crystalline aromatic polyester (A1).

First of all, there are illustrated raw materials for preparing thepolyester block copolymer (P3) in relation to the present invention No.V.

<Crystalline Aromatic Polyester (A1)>

As the crystalline aromatic polyester (A1) to be employed in the presentinvention, there can be employed the same crystalline aromatic polyester(A1) as in the present invention IV.

In components for constructing the crystalline aromatic polyester (A1),there are desirably contained not less than 50% by mol of total ofbutylene terephthalate and/or ethylene terephthalate unit inconsideration of crystallinity, heat resistance, and raw material costs.

<Lactones (B)>

As the lactones (B) to be employed for lactone-modifying the crystallinearomatic polyester (A1), there can be employed the same the lactones asin the present invention IV.

Copolymerization proportion of the crystalline aromatic polyester (A1)with respect to the lactones (B) is preferably 97/3-50/50, and morepreferably 90/10-55/45 in the weight ratio (A/B).

Further, the crystalline aromatic polyester (A1) can be allowed to reactwith the lactones (B) by heating and kneading after optionally adding acatalyst.

<Multifunctional Compound (D)>

The multifunctional compound (D) to be employed in the present inventionV is not particularly limited, if it is an aliphatic and/or aromaticcompound having at least three pieces of at least one kind of carboxylicgroup (i), hydroxyl group (ii), and/or an ester-formable group therefrom(iii) in the molecule. In the above description, the ester-formablegroup means a derivative of carboxylic group and hydroxyl group whichcan react by an esterification reaction, condensation reaction, andaddition reaction with the crystalline aromatic polyester (A1) and/orthe lactones (B) such as an ester compound from carboxylic group (i) andan ester compound from an acid chloride, an acid anhydride, and hydroxylgroup (ii).

As preferred examples of the multifunctional compound (D), there can beenumerated an aliphatic polycarboxylic acid such as butanetetracarboxylic acid; an aliphatic polyol such as glycerine, trimethylolethane, trimethylol propane (hereinafter, abbreviated as TMP), andpentaerythritol; an aromatic polycarboxylic acid such as trimesic acid,trimellitic acid, 1,2,3-benzene tricarboxylic acid, pyromellitic acid,and 1,4,5,8-naphthalene tetracarboxylic acid; an aromatic polyalcoholsuch as 1,3,5-trihydroxybenzene; an aromatic hydroxycarboxylic acid suchas 4-hydroxy isophthalic acid, 3-hydroxy isophthalic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxy benzoic acid, 2,5-dihydroxy benzoic acid,2,6-dihydroxy benzoic acid, protocatec acid, 2,4-dihydroxyphenyl aceticacid; and a compound having structural units derived from theester-formable derivatives, etc.

Hereinafter, there is illustrated the polyester block copolymer (P3) inrelation to the present invention No. V.

<Polyester Block Copolymer (P3)>

The polyester block copolymer (P3) in relation to the present inventionNo. V can be obtained by allowing to react the crystalline aromaticpolyester (A1) and the multifunctional compound (D) with the lactones(B).

The ratio (A/B) of the crystalline aromatic polyester (A1) with respectto the lactones (B) is preferably 97/3-50/50, and more preferably90/10-55/45 by weight.

In the case that the ratio of the lactones (B) is too smaller than therange, flexibility does not manifest in the polyester block copolymercomposition Q and, in the case that it is too larger than the range,heat resistance lowers.

The multifunctional compound (D) is added in a range of 0.1-100% by mol,and preferably 2-20% by mol based on 100% by mol of the crystallinearomatic polyester (A1).

In the case that addition amount of the multifunctional compound (D) isless than 0.1% by mol, dependence of melt viscosity upon extension rateis insufficient, resulting in that there cannot be obtained a moldedarticle having a uniform thickness in blow molding and, in the case thatit is larger than 100% by mol, decline of melting point is remarkable inan esterification reaction, and only identical or lower heat resistanceis obtained to or than inherent heat resistance in the polyester blockcopolymer (P3).

Reaction temperature is 180-270° C., and preferably 230-250° C.

Reaction pressure is not particularly limited, and it can be conductedat an ordinary pressure.

Reaction time of period is 0.5-180 minutes, and preferably 5-60 minutes.

Feeding order of raw materials and reaction order are not particularlylimited.

As an example of a structure in the polyester block copolymer (P3)obtained in the above-described reaction, there is enumerated astructure described below.

In the structural formula, R is a diol component, R′ is a dicarboxylicacid component, R″ is a lactone component, and R′″ is a component of themultifunctional compound. “m” is a structural unit number of thearomatic polyester, and it is 50-95, “n” is a structural unit number ofthe lactones, and it is 5-50. “1” is a structural unit number of themultifunctional compound. “1” is 0.001-1 on an average, and it has abroader range in respective compounds.

In the polyester block copolymer (P3) in relation to the presentinvention, a number average molecular weight is 30,000-100,000, amelting point is 160-250° C., and MI is 0.1-20 g/10 minutes (at 230° C.and 2.16 kgf).

Hereinafter, the epoxy compound (C) is illustrated which is allowed toreact with the polyester block copolymer (P3).

<Epoxy Compound (C)>

As the epoxy compound (C) to be employed in the present invention V, thesame epoxy compound (C) can be employed as in the present invention IV.

In the polyester block copolymer composition (Q) in relation to thepresent invention No. V, formulating amount of the epoxy compound (C) is0.5-5.0 parts by weight, and preferably 1.0-4.0 parts by weight based on100 parts by weight of the polyester block copolymer (P3). In the casethat the formulating amount is less than 0.5 part by weight, therebecomes small an effect for a general heat resistance and waterresistance in the polyester block copolymer, resulting in that athermally-aging resistance remarkably lowers. In the case that theformulating amount exceeds 5.0 parts by weight, molding processabilityoccasionally becomes worse by an influence of the unreacted epoxycompound, and there is shown a tendency that surface conditions becomecoarse in a molded article prepared.

From the same reason, two or more functional epoxy compounds must beformulated in at least 0.2 part by weight based on 100 parts by weightof the polyester block copolymer (P3).

<Carbodiimide Compound (E)>

In the present invention No. V, a carbodiimide compound (E) can beoptionally formulated with the polyester block copolymer composition(Q).

As the carbodiimide compound, for example, there is enumerated Stabaxol1 (2,6-diisopropylphenyl diisocyanate dimer) manufactured by SumitomoBayer Urethane, Ltd., etc.

Formulating amount of the carbodiimide compound is 0-2.0 parts byweight, and preferably 0.2-1.0 parts by weight based on 100 parts byweight of the polyester block copolymer (P3). If it is not formulated,there is occasionally observed a slight decline of melt viscosity duringa reaction of the epoxy compound (C), and dependence of melt viscosityupon extension rate is insufficient by an influence of an TMP amount,resulting in that there is occasionally obtained a polyester blockcopolymer composition which is not appropriate for blow molding. On theother hand, in the case that it is formulated in exceeding 2.0 parts byweight, discoloration becomes remarkable, and crystallinity lowers inthe polyester block copolymer, resulting in that heat resistance ends.to lower.

<Polyester Block Copolymer Composition (Q)>

The polyester block copolymer composition (Q) of the present invention Vis obtained by thermally kneading a formulated mixture in which thereare formulated the polyester block copolymer (P3), the epoxy compound(C), and optionally the carbodiimide compound (E).

The above-described reaction by thermally kneading is usually conductedby melt-kneading of resins and, in the case, catalysts may be employedor not employed.

As the catalysts to be employed in a reaction of the epoxy compound (C),there can be employed the same catalysts as in the present invention No.IV.

Further, temperature for melt-kneading is preferably a temperature offrom 5° C.-higher than a melting point of a crystalline in the polyesterblock copolymer (P3) to 280° C.

Kneading time of period is 30 seconds to 60 minutes or so, and it isappropriately selected depending upon a mixing style and thetemperature.

As the catalysts to be optionally added in a reaction of thecarbodiimide compound (E), all catalysts usually employed can beemployed, and the catalysts are optionally employed.

In the polyester block copolymer composition (Q) in relation to thepresent invention No. V, there can be also added the same stabilizer asin the present invention No. III.

The stabilizers may be usually in advance contained in the crystallinearomatic polyester resin (P3) which is employed as a raw materialbecause of an effect for preventing oxidation of the composition (Q) andthermal stability.

Further, there may be appropriately even added additives such aspigments and a weatherability stabilizer according to uses.

It is to be noted that the stabilizer and additives to be formulated inthe present invention may be simultaneously mixed together with theepoxy compound (C) and the carbodiimide compound (E), or may be evenindependently mixed.

In the polyester block copolymer composition (Q) of the presentinvention No. V obtained by thermally kneading, a number averagemolecular weight is 50,000-250,000, a melting point is 160-250° C., MIis 0.1-20 g/10 minutes, and a strain-hardening curability is not lessthan 0.1.

Herein, the strain-hardening curability shows a slope of a straight lineobtained by plotting ε and ln(η_(E)/3η*) when η_(E) is a value obtainedby a measurement of extension viscosity, ε is strain herein, and η* is avalue obtained by a measurement of shear viscosity.

It is to be noted that in a composition obtained, a portion of the epoxycompound may be remained within an extent at which viscosity does notincrease in kneading. Likewise, an unreacted portion of the carbodiimidecompound (E) may be also remained within an extent which can be detectedby a gas chromatography.

Hereinafter, the present invention No. VI will be illustrated in detail.

The polyester block copolymer composition of the present invention IV,in obtaining the polyester block copolymer by allowing to react thecrystalline aromatic polyester (A1) with the lactones (B), is comprisedadding and thermally-kneading 0.1-5.0 parts by weight of an epoxycompound (C) having one or more pieces of epoxy groups and 0-2.0 partsby weight of a carbodiimide compound (E) to 100 parts by weight of apolyester block copolymer (P3) obtained by allowing to react 0.1-200% bymol of at least one of a multifunctional compound (D) having at leastthree pieces of at least one kind of carboxylic group (i), hydroxylgroup (ii), and/or an ester-formable group therefrom (iii) with 100% bymol of a crystalline aromatic polyester (A1).

First of all, there are illustrated raw materials to be employed for thepreparation of the polyester block copolymer (P3) in relation to thepresent invention No. VI.

<Crystalline Aromatic Polyester (A1)>

As the crystalline aromatic polyester (A1) to be employed in the presentinvention No. VI, there can be employed a polyester having the samestructure as in the crystalline aromatic polyester (A1) in the presentinvention No. IV, and there is preferred a polyester having a meltingpoint of not less than 160° C. in the case of formation of highpolymerization degree.

Further, as a material for molding, there is preferably prepared apolyester having a number average molecular weight of not less than5,000.

Of construction components for the crystalline aromatic polyester (A1)exemplified hereinabove, there is preferably employed a polyestercontaining not less than 60% by weight of butylene terephthalate and/orethylene terephthalate units in consideration of crystallinity, heatresistance, or costs for the raw materials.

<Lactones (B)>

As the lactones (B) to be employed for lactone-modifying the crystallinearomatic polyester (A1), there can be employed the same lactones (B) asin the present invention No. IV.

Copolymerization ratio of the crystalline aromatic polyester (A1) withthe lactones (B) is the same as in the copolymerization ratio in thepresent invention No. V.

<Multifunctional Compound (D)>

As the multifunctional compound (D) to be employed in the presentinvention No. VI, there can be employed the same multifunctionalcompound (D) as in the present invention No. V.

Addition amount of the multifunctional compound (D) is 0.1-200% by mol,preferably 0.1-150% by mol based on 100% by mol of the crystallinearomatic polyester (A1).

In the case that at least one kind of the multifunctional compound (D)has carboxylic group (i) or an ester-formable group thereof, it is addedin a range of preferably 0.1-200% by mol, and more preferably 0.1-150%by mol based on 100% by mol of the crystalline aromatic polyester (A1).In the case, in the case that the addition amount of the multifunctionalcompound (D) is less than 0.1% by mol, modulus of strain hardening isinsufficient, resulting in that there is not obtained a molded articlehaving uniform thickness in blow molding and, in the case of exceeding200% by mol, a decline of a melting point is remarkable in atransesterification reaction, resulting in that there is notoccasionally obtained only a molded article having an identical or lessheat resistance inherently possessed in a polyester block copolymer.

Further, in the case of the multifunctional compound (D) not havingcarboxylic group (i) or an ester-formable group thereof, themultifunctional compound (D) is added in a range of preferably 0.1-150%by mol, and more preferably 50-120% by mol based on 100% by mol of thecrystalline aromatic polyester (A1). In the case, in the case that theaddition amount of the multifunctional compound (D) is less than 0.1% bymol, modulus of strain hardening is insufficient, resulting in thatthere is not obtained a molded article having uniform thickness in blowmolding and, in the case of exceeding 150% by mol, a decline of amelting point is remarkable in a transesterification reaction, resultingin that there is not occasionally obtained only a molded article havingan identical or less heat resistance inherently possessed in a polyesterblock copolymer. Herein, the modulus of strain hardening means acharacteristic that a melt viscosity increases when an extending rateincreases. Accordingly, when the modulus of strain hardening is larger,since a portion extended in blow molding shows a larger melt viscosity,it is not excessively extended and, since a portion extended shows alower melt viscosity, uniform thickness is obtained. Contrarily, in thecase that the modulus of strain hardening is insufficient, theabove-described effect does not manifest in blow molding, and it tendsto become difficult to obtain a molded article having a uniformthickness.

Hereinafter, there is illustrated the polyester block copolymer (P3) inrelation to the present invention No. VI.

<Polyester Block Copolymer (P3)>

The polyester block copolymer (P3) is obtained by allowing to react thecrystalline aromatic polyester (A1) and the multifunctional compound (D)with the lactones (B).

Ratio of the crystalline aromatic polyester (A1) with the lactones (B)and reaction conditions are the same as in the present invention No. V.

Subsequently, the epoxy compound (C) is illustrated which is allowed toreact with the polyester block copolymer (P3).

<Epoxy Compound (C)>

As the epoxy compound (C) to be employed in the present invention No. V,there can be employed the same epoxy compound (C) as in the presentinvention No. IV.

In the polyester block copolymer composition (Q) in relation to thepresent invention No. VI, formulation amount of the epoxy compound (C)is 0.1-5.0 parts by weight, and preferably 0.25-3.0 parts by weightbased on 100 parts by weight of the polyester block copolymer (P3). Inthe case that the formulation amount is less than 0.1 part by weight,there becomes small an effect to general heat resistance and waterresistance in the polyester block copolymer, and thermally-agingresistance remarkably lowers. In the case that the formulation amountexceeds 5 parts by weight, there is a tendency that moldingprocessability occasionally becomes worse by an influence of theunreacted epoxy compound, or surface conditions becomes coarse in amolded article.

<Carbodiimide Compound (E)>

In the present invention VI, the same carbodiimide compound (E) as inthe present invention V can be optionally formulated in the same weightratio in the polyester block copolymer composition.

<Polyester Block Copolymer Composition (Q)>

The polyester block copolymer composition (Q) of the present inventionVI is obtained by thermally kneading a blend composed of the polyesterblock copolymer (P3), the epoxy compound (C) and, optionally, thecarbodiimide compound (E).

The reaction by thermally kneading is usually conducted by melt-mixingand, in the case, catalysts may be not employed, or may be evenemployed.

As the catalysts to be employed in the reaction of the epoxy compound(C), the same catalysts can be employed as in the present invention IV.

In the composition (Q) obtained in the present invention VI, the samestabilizers can be added as in the present invention III.

Further, additives such as pigments and weatherability agents may beappropriately added depending upon uses.

Mixing of the above-described stabilizer and additives may besimultaneously or separately conducted together with mixing of theabove-described epoxy compound (C) or the carbodiimide compound (E).

In the polyester block copolymer composition (Q) of the presentinvention VI, a number average molecular weight is 40,000-110,000, amelting point is 180-230° C., and MI is 0.1-10 g/10 minutes, and it hasa large modulus of strain hardening.

As a result, it has a characteristic of an exceedingly less generationof flashes in molding, in addition to capability of providing a moldedarticle having uniform thickness in blow molding. Moreover, a moldedproduct obtained using the composition is very excellent also in heatresistance in addition to inherent properties in a polyester blockcopolymer and, even though it is employed in a use exposed to hightemperature for a long time of period, it can give a very excellentphysical property to a molded article.

Hereinafter, the present invention No. VII will be illustrated indetail.

The polyester block copolymer composition (R) of the present inventionVII, in the case of obtaining the polyester block copolymer by allowingto react the crystalline aromatic polyester (A1) with the lactones (B),is comprised heating in a solid condition a polyester block copolymercomposition (Q) obtained by adding and thermally mixing 0.1-5.0 parts byweight at least one kind of an epoxy compound (C) having one or morepieces of epoxy groups to 100 parts by weight of a polyester blockcopolymer (P) obtained by allowing to react 0.1-200% by mol of at leastone kind of a multifunctional compound (D) having at least three piecesof carboxylic group (i), hydroxyl group (ii), and/or an ester-formablegroup therefrom (iii) with respect to 100% by mol of a crystallinearomatic polyester (A).

The polyester block copolymer (P) in relation to the present inventionis obtained by a reaction of the crystalline aromatic polyester (A1)with the lactones (B).

<Crystalline Aromatic Polyester (A1)>

The crystalline aromatic polyester (A1) to be employed in the presentinvention is a polymer primarily having ester bonds, and it has hydroxylgroups at a portion of molecular terminals, and the same ones areemployed as in the present invention VI.

<Lactones (B)>

The lactones (B) to be employed in the present invention VII is the sameones as in the present invention VI.

Copolymerization proportion of the crystalline aromatic polyester (A1)with the lactones (B) is 97/3-50/50, and preferably 90/10-55/45 byweight ratio.

Further, the crystalline aromatic polyester (A) can be allowed to reactwith the lactones (B) by thermally mixing using optionally catalysts. Inthe case that the proportion of the lactones (B) is too smaller than therange, ductility does not manifest in the polyester block copolymer (P),and in the case of being too larger than the range, heat resistancelowers in the polyester block copolymer (P) and the polyester blockcopolymer composition (R) obtained.

<Multifunctional Compound (D)>

The multifunctional compound (D) to be employed in the present inventionis the same as in the present invention No. VI.

Addition amount of the multifunctional compound (D) is 0.1-200% by mol,preferably 0.1-150% by mol based on 100% by mol of the crystallinearomatic polyester (A).

In the case that the multifunctional compound (D) does not havecarboxylic group (i) or an ester-formable group thereof, it is added ina range of preferably 0.1-150% by mol, and more preferably 50-120% bymol based on 100% by mol of the crystalline aromatic polyester (A1). Inthe case that the addition amount of the multifunctional compound isless than 0.1% by mol, the modulus of strain hardening is insufficient,resulting in that there is not obtained a molded article having uniformthickness in blow molding and, in the case of exceeding 150% by mol, adecline of a melting point is remarkable in a transesterificationreaction, resulting in that there is not occasionally obtained only amolded article having an identical or less heat resistance inherentlypossessed in a polyester block copolymer.

Further, in the case that the multifunctional compound (D) has at leastone of carboxylic group (i) or an ester-formable group thereof, it isadded in a range of preferably 0.1-200% by mol, and more preferably50-150% by mol based on 100% by mol of the crystalline aromaticpolyester (A1). In the case that the addition amount of themultifunctional compound is less than 0.1% by mol, the modulus of strainhardening is insufficient, resulting in that there is not obtained amolded article having uniform thickness in blow molding and, in the caseof exceeding 200% by mol, a decline of a melting point is remarkable ina transesterification reaction, resulting in that there is notoccasionally obtained only a molded article having an identical or lessheat resistance inherently possessed in a polyester block copolymer.

Subsequently, there will be illustrated the polyester block copolymer(P) in relation to the present invention.

<Polyester Block Copolymer (P)>

The polyester block copolymer (P) in relation to the present inventionis obtained by allowing to react the crystalline aromatic polyester (A1)having terminal hydroxyl groups, the multifunctional compound (D), andthe lactones (B).

Reaction temperature is 180-270° C., and preferably 230-250° C.

Reaction pressure is not particularly limited, and reaction can beconducted at an ordinary pressure.

Reaction time of period is 0.5-600 minutes, and preferably 5-120minutes.

Feeding order of raw materials and reaction order are not particularlylimited.

In the polyester block copolymer composition (P) in relation to thepresent invention, a number average molecular weight is 20,000-100,000,a melting point is 160-250° C., and MFR is 0.1-50 g/10 minutes (230° C.,2.16 kgf).

The epoxy compound (C) to be allowed to react with the polyester blockcopolymer (P) is the same as in the present invention VI.

Formulation amount of the epoxy compound (C) is 0.1-5.0 parts by weight,and preferably 0.25-3.0 parts by weight based on 100 parts by weight ofa polyester block copolymer (P). In the case that the formulation amountis less than 0.1 part by weight, there becomes small an effect togeneral heat resistance and water resistance in the polyester blockcopolymer, and thermally-aging resistance remarkably lowers. In the casethat the formulation amount exceeds 5.0 parts by weight, there is atendency that molding processability occasionally becomes worse by aninfluence of the unreacted epoxy compound, or surface conditions becomescoarse in a molded article.

<Polyester Block Copolymer Composition (Q)>

The polyester block copolymer composition (Q) of the present inventionVI is obtained by thermally kneading a mixture composed of the polyesterblock copolymer (P) and the epoxy compound (C).

Mixing of the epoxy compound (C) with the polyester block copolymer (P)is usually conducted by melt-mixing and, a method for the mixing is notlimited at all, if it is a method capable of uniformly mixing, anymethods may be applied.

Temperature in melt-mixing of the epoxy compound ranges in preferably 3°C.- to 60° C.-higher temperature, and more preferably 5° C.- to 40°C.-higher temperature than a melting point of the polyester blockcopolymer. In the case that the temperature in melt-mixing is higher,decomposition reaction is thermally accelerated, whereby, resulting inthat heat resistance, hydrolysis resistance, and color hue become worse.In the case that the temperature in melt-mixing is lower, dispersionconditions of the epoxy compound become worse. Time of period inmelt-mixing is 10 second to 10 minutes or so, preferably, it is set upin 30 second to 5 minutes. Compared to a conventional method, that is, amethod by melt-mixing alone, since a treatment at a lower temperaturecan be conducted and evaporation components can be decreased, a workingcircumstance can be improved.

<Polyester Block Copolymer Composition (R)>

Conditions are as follows at which the polyester block copolymercomposition (Q) is thermally treated in a solid phase for obtaining thepolyester block copolymer composition (R).

As the conditions for thermally treating in a solid phase, heatingtemperature (Ta) ranges in from a lower temperature than a melting pointof the polyester block copolymer composition (R) to a higher temperaturethan a glass transition point of the polyester block copolymercomposition (R) under an inert gas atmosphere and, moreover, it is ahigher temperature than 120° C.

Tg<Ta<Tm(R),

and

120° C.<Ta

In the case that the epoxy compound (C) contains at least one kind of abifunctional epoxy compound, heating temperature (Ta) in a solid phaseis 10° C.- to 5° C.-lower than a melting point of a polymer in a solidphase and higher than 150° C.

Tm(R)−100° C.≦Ta≦Tm(R)−5° C.,

and

150° C.≦Ta

Heating in a solid phase can be conducted by two stages described below.

(1) after having preheated at a temperature (Tb) lower than 150° C. andlower than Ta which is in a temperature range from a temperature lowerthan a melting point of a polymer in a solid phase to a temperaturehigher than a glass transition point of the polymer,

(2) heated at a temperature (Ta) which is in a temperature range from atemperature lower than a melting point of a polymer in a solid phase toa temperature higher than a glass transition point of the polymer, andhigher than 120° C.

Preheating temperature Tb

Tg<Tb<Tm(R),

Tb<150° C.,

and

Tb≦Ta

Heating temperature Ta

Tg<Ta<Tm(R),

and

120° C.<Ta

In the case, catalysts may be not employed or even employed.

As the catalysts, there can be employed all catalysts which can beusually employed in a reaction of epoxy compounds. For example, therecan be employed solely or in combination of amines, phosphoruscompounds, salts of a monocarboxylic acid or a dicarboxylic acid havinga carbon number of not less than 10 with metals in the Ia and IIa groupsof elementary periodic table. Such the catalysts may simultaneously addtogether with the epoxy compound, or may even add after having inadvance dispersed the epoxy compound into the polyester block copolymerin a melting state or, contrarily, the catalysts may be in advance evendispersed.

In the polyester block copolymer composition (R) of the presentinvention, an acid value is not more than 0.5 mgKOH/g, a melting pointTm (R) is a temperature of not more than 5° C.-lower temperature than amelting point Tm (P) in the polyester block copolymer composition (P)before adding the epoxy compound.

Tm(R)≧Tm(P)−5° C.

In the polyester block copolymer composition, a temperature for an MIvalue test is not less than 5° C.-higher than a melting point of thecomposition, and it is a lowest temperature of an experimentaltemperature described in Table 1 of JIS K7210 and, moreover, a meltviscosity stability {(MI−B)/(MI−A)} is 0.5-2.0, which is calculated froman MI value (MI−A) measured at experimental conditions selected so thatan experimental loading becomes a range of an MI value of 1-30 g/10minutes and an MI value (MI−B) at the same experimental temperature andthe same experimental loading as in a measurement of the (MI−A) afterheating for 10 minutes from an initiation of measurement of the MI−Avalue at the same experimental temperature as in a measurement of theMI−A value.

In the polyester block copolymer composition (R), a number averagemolecular weight is 40,000-200,000, a melting point is 150-280° C., MIis 0.01-5, and modulus of a strain-hardening is not less than 0.1-2.4.Herein, the modulus of a strain-hardening shows a slope of a straightline obtained by plotting ε and ln(η_(E)/3η*) when η_(E) is a valueobtained by a measurement of extension viscosity, ε is strain herein,and η* is a value obtained by a measurement of shear viscosity.

In the polyester block copolymer composition (R), there can be added astabilizer such as a hindered phenol-based compound, a phosphite-basedcompound or an organic composite phosphite, and a carbodiimide compound.Since the stabilizers have an effect for prevention of oxidation orthermal stability in the polyester block copolymer composition, thoseare usually added to polyester-based resins. Further, additives such aspigments and weatherability stabilizers may be appropriately even addeddepending upon uses.

Mixing of the stabilizers and additives to be formulated in the presentinvention may be simultaneously conducted when the epoxy compound ismixed, or may be even independently conducted.

In the polyester block copolymer composition (R) obtained in the presentinvention, the modulus of strain hardening is large, and there can beobtained a molded article having uniform thickness in blow molding and,further, a change ratio of melt viscosity by thermal history is smalland a resin can be reused. Further, color hue is more improved than in areaction proceeded in a melting state owing to a characteristic that areaction with the epoxy compound (C) is conducted by heating in a solidphase and, furthermore, a large melt viscosity can be obtained,resulting in that a large-size molded article can be also obtained inblow molding. Also, it has a characteristic that production of flashesin molding is exceedingly slight. Moreover, a molded article obtainedusing the composition (R) is very excellent also in heat resistance inaddition to properties shown in a polyester block copolymer and, eventhough it is employed for uses exposed to a high temperature for a longtime of period, it does not cause heat deterioration, and it can providea molded article having very excellent physical properties.

EXAMPLES

Hereinafter, although the present invention will be specificallyillustrated by Examples, the present invention is not limited thereto.In the Examples, mere part means part by weight.

Hereinafter, there were measured as follows an acid value, an unreactedlactone amount, a polycaprolactone content in resins, an MI value, amelt viscosity stability, a tensile strength and extension, thermalproperties (a melting point, a melting peak temperature, an initiatingtemperature of melting), color hue, hydrolizability, and heat resistancestability.

Unreacted Lactone Amount

Using GC-14A manufactured by Shimadzu, there was employed a glass-madecolumn having an internal diameter of 3.2 mm and length of 2.1 m, and inwhich there is filled [PEG20M (a liquid for a fixed bed) 10%]/[UniportHPS (carrier)]. 1 g of a sample and 0.05 g of diphenylether which is aninternal standard substance were precisely weighed, followed bydissolving into HFIP (hexafluoroisopropanol). Measurement was conductedat the constant temperature of 180° C. using nitrogen as a carrier gas,unreacted lactone amount (% by weight) was calculated by an internalstandard method based on results obtained. Polycaprolactone content inthe polyester block copolymer (P1):

The residual unreacted lactone was removed from the polyester blockcopolymer (P1), and a polymer obtained was dissolved in a solventHFIP/CDCl₃ (heavy chloroform)=9/1 which contains a small amount oftetramethylsilane, and there was measured the component ratio of apolybutylene terephthalate with respect to a polycaprolactone by aproton NMR.

It was confirmed that the polycaprolactone content in the polyesterblock copolymer (P1) is in a range of 59.9/40.1 to 60.3/39.7 in allresins in the present invention I.

MI Value

It was measured at a sample temperature of 230° C. in heating and aloading of 2,160 kgf according to JIS K7210.

The above value are employed even as a value of T:230° C. and P:2,160kgf in the following MI value (T, p, t).

Melt Viscosity Stability

The melt viscosity stability is shown by MI (T, p, t+10)/MI (T, p, t).In the equation, the Melt Index (MI (T, p, t)) value is a value at aheating temperature (T), loading (P), and heating time of period (t)which are described in the JIS K7210, and T is not less than 5°C.-higher temperature than a melting point of the composition (R), andit is a lowest temperature of experimental temperature described inTable 1 of the JIS K7210. P is a value selected so that MI value becomesa range of 1-30 g/10 minutes.

MI (T, P, t+10) is a value when heating time of period is set up at t+10minutes in the above conditions T and P.

In the Examples described below, specifically, T is 230° C., P is 2.16kgf, and “t” is a time of period regulated in JIS.

Tensile Strength and Extension

Tips were molded into a plain plate having the thickness of 2 mm using aheating press, and Dumbbell No. 3 test piece was punched, and the testpiece was extended at the speed of 200 m/minutes, and strength is shownby a value in which a load (kgf) at break is divided by an initial crosssectional area (cm₂), the extension ratio (%) is a proportion ofextension in the original test piece with respect to length of anoriginal test sample.

Melting Point

Melting point is a peak temperature in melting measured by adifferential scanning calorimeter (DSC) apparatus according to JISK7121.

Color Hue

Yellow Index (YI) value was measured by a color difference meter Σ-90manufactured by Nihon Denshoku Kogyo.

Acid Value

Sample was dried at 100° C. and a reduced pressure for 20 hours,followed by weighing 1.0 g and thermally dissolving in 50 g of benzylalcohol at 160° C. After having cooled by water, 50 g of chloroform wasadded and mixed. Using phenol phthalein as an indicator, titration wasconducted by a 1/10 normal KOH ethanol solution. There were decidedvalues at 0 minute by an extrapolation method from appropriate threepoints in which dissolving time of period is 10-30 minutes and, a valuein which an acid value in a mixture of benzyl alcohol with chloroformwas taken off from the values employed as an acid value (mgKOH/g) of thesamples. The acid value in the mixture was separately measured.

Hydrolysis Resistance

The plain plate having the thickness of 2 mm prepared by molding thetips using a heating press was immersed in hot water of 95° C. for 7days to hydrolyze, and Dumbbell No. 3 test pieces were punched from theplate. Test pieces were extended at speed of 200 mm/minute, a value inwhich load (kg) at break was divided by an initial cross sectional area(cm₂) is shown as a strength (kg/cm₂), and the extension ratio (%) isshown as a proportion of extension in the test piece until a break withrespect to length of an original test sample. The extension ratio in thecase of not conducting a hydrolysis treatment is shown as 100%, and itis compared to an extension ratio in the case of having broken.

Heat Resistance Stability

The plain plate having the thickness of 2 mm prepared by molding thetips using a heating press was placed in a gear oven adjusted to 165° C.for 14 days to thermally-treat, and Dumbbell No. 3 test pieces werepunched from the plate. Test pieces were extended at speed of 200mm/minute, and a value in which load (kgf) when having broken wasdivided by an initial cross sectional area (cm₂) is shown as a strength(kgf/cm₂), and the extension ratio (%) is shown as a proportion ofextension in the test piece until a break with respect to length of anoriginal test sample. The extension ratio in the case of not beingthermally treated is shown as 100%, and it is compared to an extensionratio in the case of having broken.

Modulus of Strain Hardening

It is shown as a slope of a straight line obtained by plotting ε andln(η_(E)/3η*) when η_(E) is a value obtained by a measurement ofextension viscosity at a constant strain rate and 230° C., e is strainherein, and η* is a value obtained by a measurement of shear viscosity.Results are shown as follows. In the case that the slope is not lessthan 1.0, a sample shows (⊚) the modulus of strain hardening, in thecase that the slope is less than 1.0, a sample slightly shows (∘) themodulus of strain hardening, and in the case that the slope is 0, asample does not show (x) the modulus of strain hardening. It is to benoted that it is shown by a value in the case of the present inventionVII.

Draw Down Property

Capirograph manufactured by Toyo Seiki was equipped with a capillaryhaving a diameter of 3 mm and length of 10 mm, and a resin was extrudedat 240° C. and an extruding rate of 20 mm/min. A time of period when astrand is 300 mm-extended was compared to a time of period when a strandis 60 mm-extended to calculate the ratio. For blow molding, it ispreferred that the ratio is not less than 3.

Feeding Molar Ratio (A:D):

Addition ratio % by mol of the multifunctional compound (D) wascalculated from a number average molecular weight of the polyester (A)measured by GPC based on a standard polymethyl methacrylate (PMMA), anda formulating mol amount of the (A) was decided based thereon. Supposingthat the formulating mol amount of the (A) is 100% by mol, the additionratio % by mol of the multifunctional compound (D) is decided in a rangeof 0.01-5.0% by mol depending upon uses.

As a column in the GPC, there were employed Shodex GPC HFIP-800P,HFIP-805P, HFIP-804P, and HFIP-803P manufactured by Showa Denko, Ltd.,and RID-6A manufactured by Shimadzu Seisakusyo was employed as adetector. As an elution liquid, hexafluoro isopropanol was employed, anda measurement was conducted at a column temperature of 50° C. and a flowrate of 1.0 ml/min.

<Raw Material>

Crystalline Aromatic Polyester

As the crystalline aromatic polyester, there was employed a polybutyleneterephthalate (PBT) described below having hydroxyl groups at terminalsof a molecule.

PBT (A1) employed in the present invention I is a commercially suppliedpolybutylene phthalate having a melting point of approximately 230° C.which is composed of terephthalic acid and isophthalic acid which are anacid component and 1,4-butane diol which is a glycol component, andwhich has a number average molecular weight of 39,000.

PBT (A1) employed in the present invention II is a commercially suppliedpolybutylene phthalate having a melting point of approximately 230° C.which is composed of terephthalic acid and isophthalic acid which are anacid component and 1,4-butane diol which is a glycol component, andwhich has a number average molecular weight of 35,000.

PBT (A1) employed in the present invention III is a commerciallysupplied polybutylene phthalate having a melting point of approximately230° C. which is composed of terephthalic acid and isophthalic acidwhich are an acid component and 1,4-butane diol which is a glycolcomponent, and which has a number average molecular weight of 31,000.

PBT (A₁) employed in the present invention IV is a commercially suppliedpolybutylene phthalate having a melting point of approximately 205° C.which is composed of terephthalic acid and isophthalic acid which are anacid component and 1,4-butanediol which is a glycol component, and whichhas a number average molecular weight of 35,000.

Likewise, PBT (A₂) is a commercially supplied polybutylene phthalatehaving a melting point of approximately 185° C. which is composed ofterephthalic acid and isophthalic acid which are an acid component and1,4-butanediol which is a glycol component, and which has a numberaverage molecular weight of 35,000.

PBT (A1) employed in the present invention V is a commercially suppliedpolybutylene phthalate having a melting point of approximately 230° C.which is composed of terephthalic acid and isophthalic acid which are anacid component and 1,4-butanediol which is a glycol component, and whichhas hydroxyl groups at terminals of a molecule and has a number averagemolecular weight of 39,000. However, PBT (A1) employed in ComparativeExample V-I is a commercially supplied polybutylene phthalate having amelting point of approximately 230° C. which is composed of terephthalicacid and isophthalic acid which are an acid component and 1,4-butanediolwhich is a glycol component, and which has a number average molecularweight of 35,000.

PBT (A₁) employed in the present inventions VI and VII is a commerciallysupplied polybutylene phthalate having a melting point of approximately230° C. which is composed of terephthalic acid and isophthalic acidwhich are an acid component and 1,4-butanediol which is a glycolcomponent, and which has a number average molecular weight of 39,000.

Abbreviations of Substances to be Formulated

Phenylglycidyl ether (GPE)

Kardular E-10 (a glycidyl type monoepoxy compound)

Bisphenol F diglycidyl ether (BFDGE)

Cyclohexane dicarboxylic acid diglycidyl ester (CHDDG)

3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Clloxide2021P manufactured by Daicel Chemical Industries, Ltd.)

Triphenylphosphine (TPP)

Tetraxis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate]methane(a trade name: Irganox 1010)

Reaction Vessel for Synthesis of a Polyester Block Copolymer

As the reaction vessel for synthesis of a polyester block copolymer,there was employed a vessel equipped with an agitator, a thermometer, acondenser, and a line for distilling out.

Extruder for Kneading

There was employed a 32 mm ø twin-screw extruder (merely abbreviated asan extruder).

Conditioned Test Piece

From a polyester block copolymer composition, a sheet having thicknessof 1 mm was prepared by compression molding, and a tensile test piecehaving thickness of 1 mm was prepared by punching, which is shown in JISK7113 No. 2.

The test piece was placed in an oven set up at a temperature of 140° C.,and sampling was conducted with a time lapse, and it was employed as aconditioned test sample after having placed in a room conditioned at 25°C. and 50 RH% for 24 hours.

Hereinafter, Examples are illustrated in relation to the presentinvention I.

Examples I-1 to I-3

60 kg of a sufficiently dried polybutylene terephthalate chips wereheated to 140° C. in a batch type tank type reaction vessel, and therewere supplied 42.6, 41.2, and 40.8 kg of ε-caprolactone heated to 200°C., respectively, into the vessel. While agitating at 230° C. under anitrogen gas atmosphere, a reaction was conducted, respectively. At aperiod at which average concentration of unreacted lactone intends tobecome 2.53, 1.19, and 0.79% by weight, respectively, pellet like resinswere taken out to measure an amount of the unreacted lactone and an acidvalue. The resins obtained were further placed under a reduced pressureat 120° C. in a pellet like to remove the unreacted lactone and tomeasure a melting point and an MI value. Results are collectively shownin Table I-1.

Comparative Example I-1

The same procedures were followed as in the Example I-1 except thatε-caprolactone to be employed was changed to 40.4 kg and averageconcentration of unreacted lactone becomes 0.40% by weight to take out aresin and to analyze. Results are collectively shown in Table I-1.

Examples I-4 to I-6

A twin-screw extruder was equipped with a hopper and a screw stylefeeder at an upper portion. Likewise as in the Example I-1, asufficiently dried polybutylene terephthalate chips were filled in thehopper, and maintained under a nitrogen atmosphere. An equipment forcharging ε-caprolactone was equipped at a portion of the twin-screwextruder, and a tank which is maintained under a nitrogen atmosphere wasconnected through a pump. Operating conditions of apparatuses wereadjusted so that a temperature of a mixed liquid discharged from theextruder is maintained at 230° C.

Resins continuously discharged from the twin-screw extruder werecontinuously fed to a twin-screw continuous kneader having kneadingdiscs (KRC manufactured by Kurimoto Tekkosyo), and operating conditionsof apparatuses were adjusted so that a resin temperature is maintainedat 230° C.

Weight ratio of the polybutylene terephthalate resin with respect toε-caprolactone was fixed at 42.6, 41.2, and 40.8, respectively, withrespect to 60 of the polybutylene terephthalate and, at a period atwhich average concentration of unreacted lactone becomes 2.53, 1.19, and0.79% by weight, respectively, pellet like resins were taken out tomeasure the amount of the unreacted lactone and an acid value. Theresins obtained were further placed at a reduced pressure and 120° C. toremove the unreacted lactones and to measure a melting point and an MIvalue.

Results are collectively shown in Table 1-2.

Comparative Example I-2

The same procedures were followed as in the Example I-4 except that theweight ratio of the polybutylene terephthalate resin with respect toε-caprolactone was fixed at 40.4 with respect to 60 of the polybutyleneterephthalate and average concentration of the unreacted lactone inresins discharged is maintained 0.40% by weight to likewise analyze.Results are collectively shown in Table I-2.

Examples I-7 to I-9 and Comparative Example I-3

The same procedures were followed as in the Examples I-4 to I-6 andComparative Example I-2 except that temperature of respective resins tobe discharged is adjusted to 236° C. in a twin screw extrude and acontinuous kneader. Results are collectively shown in Table I-3.

TABLE I Example Example Example Comparative I-1 I-2 I-3 Example I-1Reaction min 54 77 94 132 time of period Concen- Weight % 2.61 1.22 0.800.45 tration of Unreacted lactone Acid value mgKOH/g 1.80 1.80 2.05 2.45Peak ° C. 204.4 203.7 202.3 198.3 Tempera- ture in Melting (Tm)Initiating ° C. 189.0 187.9 185.8 180.7 tempera- ture Of melting (Tim)MI value g/10 min 2.5 2.8 3.2 4.5 Example Example Example ComparativeI-4 I-5 I-6 Example I-2 Reaction min 49 67 81 112 time of Period Concen-Weight % 2.60 1.21 0.81 0.43 tration of Unreacted lactone Acid valuemgKOH/g 1.75 1.75 1.85 2.25 Peak ° C. 207.4 206.4 205.2 203.1 Tempera-ture in Melting (Tm) Initiation ° C. 192.0 190.5 188.8 184.7 tempera-ture Of melting (Tim) MI value g/10 min 2.4 2.5 2.8 3.4 Example ExampleExample Comparative I-7 I-8 I-9 Example I-3 Reaction min 40 55 68 98time of Period Concen- Weight % 2.60 1.21 0.81 0.43 tration of Unreactedlactone Acid value mgKOH/g 1.85 1.90 2.00 2.55 Peak ° C. 205.2 204.5203.5 201.7 Tempera- ture in Melting (Tm) Initiating ° C. 190.1 188.9187.2 183.0 tempera- ture Of melting (Tim) MI value g/10 min 2.4 2.5 3.25.4

By the present invention I, in the case of obtaining a polyester blockcopolymer (P1) from a crystalline aromatic polyester and lactones, itwas confirmed that there can be obtained the polyester block copolymer(P1) having a higher molecular weight which is excellent in heatresistance and hydrolyzability by remaining a fixed amount of unreactedlactones in the polyester block copolymer (P1).

Further, there was able to be confirmed an effect for elevating areaction rate of the crystalline aromatic polyester (A1) with lactones(B) by increasing an amount of the unreacted lactones.

Hereinafter, Examples are illustrated in relation to the presentinvention II.

Examples II-1 to II-3

60 kg of a sufficiently dried polybutylene terephthalate chips wereheated to 140° C. in a batch type tank type reaction vessel, and therewere supplied 42.6, 41.2, and 40.8 kg of ε-caprolactone heated to 200°C., respectively, into the vessel. While agitating at 230° C. under anitrogen gas atmosphere, a reaction was conducted, respectively. At aperiod at which average concentration of unreacted lactone intends tobecome 2.53, 1.19, and 0.79% by weight, respectively, pellet like resinswere taken out to measure an amount of the unreacted lactone and an acidvalue. The pellet like resins obtained were further allowed to react ina flask equipped with agitating blades at 165° C. in a solid phase andcooled after 20 hours to measure a melting point and an MI value.Results are collectively shown in Table II-1.

Comparative Example II-1

The same procedures were followed as in the Example II-1 except thatε-caprolactone to be employed was changed to 40.4 kg and averageconcentration of unreacted lactone becomes 0.40% by weight to take out aresin in a pellet state and to analyze. Results are collectively shownin Table II-1.

Examples II-4 to II-6

A twin-screw extruder was equipped with a hopper and a screw stylefeeder at an upper portion. Likewise as in the Example 1, a sufficientlydried polybutylene terephthalate chips were filled in the hopper, andmaintained under a nitrogen atmosphere. An equipment for chargingε-caprolactone was equipped at a portion of the twin-screw extruder, anda tank which is maintained under a nitrogen atmosphere in whichε-caprolactone was filled was connected through a pump. Operatingconditions of apparatuses were adjusted so that a temperature of a mixedliquid discharged from the extruder is maintained at 230° C. Resinscontinuously discharged from the twin-screw extruder were continuouslyfed to a twin-screw continuous kneader having kneading discs (KRCmanufactured by Kurimoto Tekkosyo), and operating conditions ofapparatuses were adjusted so that a resin temperature is also maintainedat 230° C.

Weight ratio of the polybutylene terephthalate resin with respect toe-caprolactone was fixed at 42.6, 41.2, and 40.8, respectively, withrespect to 60 of the polybutylene terephthalate and, at a period atwhich average concentration of unreacted lactone becomes 2.53, 1.19, and0.79% by weight, respectively, pellet like resins were taken out tomeasure the amount of the unreacted lactone and an acid value. Thepellet state resins obtained were further allowed to react in a solidphase at reduced pressure of 0.5 torr and 165° C. in a flask equippedwith agitating blades and cooled after 20 hours to remove the unreactedlactones and to measure a melting point and an MI value. Results arecollectively shown in Table II-2.

Comparative Example II-2

The same procedures were followed as in the Example II-4 except that theweight ratio of the polybutylene terephthalate resin with respect toε-caprolactone was fixed at 40.4 with respect to 60 of the polybutyleneterephthalate and average concentration of the unreacted lactone inresins discharged is maintained 0.40% by weight to likewise analyze.Results are collectively shown in Table II-2.

Examples II-7 to II-9 and Comparative Example II-3

The same procedures were followed as in the Examples, II-4 to II-6 andComparative Example II-2 except that respective temperatures of resinsto be discharged from the twin-screw extruder and the twin-screwcontinuous kneader were adjusted to 236° C. and the reactiontemperatures in a solid phase was adjusted to 170° C., and reaction timeof period in a solid phase was adjusted to 15 hours. Results arecollectively shown in Table II-3.

TABLE II Example Example Example Comparative II-1 II-2 II-3 Example II-1Reaction min 42 58 72 118 time of Period at first step Concen- Weight %2.50 1.21 0.81 0.43 tration of Unreacted lactone Acid value mgKOH/g 2.752.80 3.00 3.45 Peak ° C. 203.3 202.8 201.2 197.4 Tempera- ture inMelting (Tm) Initiation ° C. 187.7 186.6 184.4 179.2 tempera- ture Ofmelting (Tim) MI value g/10 min 7.0 8.2 10.2 14.8 Example ExampleExample Comparative II-4 II-5 II-6 Example II-2 Reaction min 34 45 55 85time of Period at first step Concen- Weight % 2.53 1.20 0.80 0.41tration of Unreacted lactone Acid value mgKOH/g 2.55 2.60 2.85 3.30 Peak° C. 206.5 205.3 204.4 202.3 Tempera- ture in Melting (Tm) Initiation °C. 190.7 189.2 187.3 183.2 tempera- ture Of melting (Tim) MI value g/10min 5.4 7.0 9.3 12.1 Example Example Example Comparative II-7 II-8 II-9Example II-3 Reaction min 26 34 41 66 time of Period at first stepConcen- Weight % 2.55 1.22 0.81 0.40 tration of Unreacted lactone Acidvalue mgKOH/g 2.55 2.65 2.90 3.50 Peak ° C. 204.1 203.5 202.3 200.9Tempera- ture in Melting (Tm) Initiation ° C. 188.9 187.3 185.8 181.5tempera- ture Of melting (Tim) MI value g/10 min 5.2 6.8 8.9 12.9

The polyester block copolymer having a high molecular weight obtained bythe present invention II has a higher melting point than that of acopolymer obtained by conventional methods and, particularly, in whichbroadening of a low melting point portion can be reduced in a meltingpeak and, whereby, there was able to be obtained a polyester blockcopolymer which is excellent in heat resistance and moldingprocessability and has a higher viscosity and molecular weight.

Hereinafter, Examples are illustrated in relation to the presentinvention III.

Preparation Example III-1

(Preparation of a Polyester Block Copolymer [TPEE (PA-1)])

60 kg of a commercially supplied PBT ( ) and 40 kg of ε-caprolactonewere fed in a reaction vessel, followed by allowing to react in amelting state at 235° C. for 2 hours after purging nitrogen. After that,unreacted ε-caprolactone was removed at a reduced pressure, and a strandstate resin was taken out of a valve set up at a bottom of the reactionvessel with a gear pump, followed by molding into pellets. In the resinobtained, an MI value was 15.2 g/10 minutes, tensile strength was 290kg/cm², and extension at break was 680%. A melting point was 203.5° C.,and an acid value was 1.5 mgKOH/g, and color hue was YI of 15.

Preparation Example III-2

(Preparation of a Polyester Block Copolymer [TPEE (PA-2)])

There were heated 2390 parts of dimethylterephthalate, 1460 parts of apoly(tetramethylene)glycol having a number average molecular weight of1400, and 1664 parts of 1,4-butanediol together with 0.04% (based ontotal of raw resin materials) of titanium tetrabutoxide which is acatalyst at 210° C. for 2 hours to distill off 95% of a theoreticalamount of methanol to an outside of a system.

Subsequently, temperature was raised to 245° C., and internal pressureof a system was reduced to not more than 0.2 mm Hg over 50 minutes, andpolymerization was conducted for 3 hours under the conditions. Afterthat, a strand state resin was taken out of a valve set up. at a bottomof the reaction vessel with a gear pump, followed by molding intopellets. In the resin obtained, an MI value was 16.1 g/10 minutes,tensile strength was 310 kg/cm², and extension at break was 620%. Amelting point was 210.4° C., and an acid value was 1.2 mgKOH/g, andcolor hue was YI of 21.

Examples III-1 to III-6

Into 100 parts by weight of a polyester block copolymer (PA-1) or (PA-2)obtained hereinabove, there were added after weighing compounds selectedfrom GPE, Kardula-ε-10, TPP, sodium stearate, and Irganox 1010 in theweight part described in Table III-1, respectively, followed by mixingin a drum tumbler at a room temperature for 30 minutes. Mixture wasmelt-mixed using an extruder at 230° C. for a heating time of 1 minute,extruded, and cut after cooled in water to pelletize. Pellets obtainedwere fed into a tank type apparatus which can be heated and agitated,and can be pressure-reduced and purged by nitrogen, and preheated atconditions of 100° C. and 100 torr for 3 hours. Further, the apparatuswas purged by nitrogen and returned to an ordinary pressure, and athermal treatment was conducted at 180° C. for a time of period shown inTable III-1, respectively. After the treatment, the apparatus was cooledunder nitrogen, and pellets were taken out to measure respectivephysical properties and analytical values.

Conditions and measurement results are shown in Table III-1.

In the Table, there are obtained resins, in which a decline of color hueand viscosity is low, and which has excellent physical properties, andin which an acid value can be reduced by a small amount of the epoxycompounds. Further, volatile components in melt-mixing were less in allExamples compared to the Comparative Examples.

Comparative Examples III-1 to III-8

Into 100 parts by weight of a polyester block copolymer (PA-1) or(PA-2), there were added after weighing compounds selected from GPE,Kardular ε-10, TPP, sodium stearate, and Irganox 1010 in the weight partdescribed in Table III-2, respectively, followed by mixing in a drumtumbler at a room temperature for 30 minutes.

Mixture was melt-mixed while controlling a feeding amount using anextruder at a temperature shown in Table III-2 extruded, and cut aftercooled, respectively, in water to pelletize.

Respective physical properties and analytical values were measured inrelation to the pellets obtained. Conditions and measurement results areshown in Table III-2. From the Table, it was confirmed that a largeamount of the epoxy compounds are required in order to sufficientlylower an acid value, and it is supposed that there become worse physicalproperties such as color hue and viscosity.

Examples III-7 to III-10

Into 100 parts by weight of a polyester block copolymer (PA-1), therewere added after weighing compounds selected from GPE, Kardular ε-10,TPP, sodium stearate, and Irganox 1010 in the weight part described inTable III-3, respectively, followed by mixing in a drum tumbler at aroom temperature for 30 minutes. Mixture was melt-mixed using anextruder at 230° C. for a heating time of 1 minute, extruded, and cutafter cooled in water to pelletize.

Pellets obtained were fed into a tank type apparatus which can be heatedand agitated, and can be pressure-reduced and purged by nitrogen, andpreheated at conditions of 100° C. and 100 torr for 2 hours. Further,the apparatus was purged by nitrogen and returned to an ordinarypressure, and a thermal treatment was conducted at 180° C. for a time ofperiod shown in Table III-3, respectively.

After the treatment, the apparatus was cooled under nitrogen, andpellets were taken out to measure respective physical properties andanalytical values. Conditions and measurement results are shown in TableIII-3. In the Table, there are obtained resins and, in which an acidvalue can be reduced by a small amount of the epoxy compounds and, inwhich viscosity is sufficiently elevated and an elevation of viscosityby remelting is less, and which has excellent color hue and physicalproperties.

Comparative Examples III-9 to III-13

Into 100 parts by weight of a polyester block copolymer (PA-1), therewere weighed compounds selected from GPE, Kardular E-10, TPP, sodiumstearate, and Irganox 1010 in the weight part described in Table III-4,respectively, followed by mixing in a drum tumbler at a room temperaturefor 30 minutes. Mixture was melt-mixed while controlling a feedingamount using an extruder at a temperature of 260° C. for 5 minute,extruded, and cut after cooled in water to pelletize. Respectivephysical properties and analytical values were measured in relation tothe pellets obtained. Conditions and measurement results are shown inTable III-4. From the Table, it was confirmed that a large amount of theepoxy compounds are required in order to sufficiently lower an acidvalue, and an elevation of viscosity is not sufficiently caused, and anelevation of viscosity by reheating is large.

Example III-11

Into 100 parts by weight of a polyester block copolymer (PA-1), therewere weighed compounds selected from GPE, BFDGE, TPP, and Irganox 1010in the weight part described in Table III-3, respectively, followed bymixing in a drum tumbler at a room temperature for 30 minutes. Mixturewas melt-mixed using an extruder at 230° C. for a heating time of 1minute, extruded, and cut after cooled in water to pelletize. Pelletsobtained were fed into a tank type apparatus which can be heated andagitated, and can be pressure-reduced and purged by nitrogen, andelevated to 180° C. at an ordinary pressure, and a thermal treatment wasconducted for 10 hours. After cooled under nitrogen, and pellets weretaken out to measure respective physical properties and analyticalvalues.

Conditions and measurement results are shown in Table III-3.

TABLE III Example Example Example Example Example Example III-1 III-2III-3 III-4 III-5 III-6 TPEE Kind PA-1 PA-1 PA-1 PA-1 PA-1 PA-2 GPE PBW0.9 0.9 0.9 CE-10 ^(*1) PBW 1.5 1.5 1.5 TPP PBW 0.1 0.1 St-Na ^(*2) PBW0.1 0.1 0.1 0.1 IR ^(*3) PBW 0.5 0.5 Preheating Temperature 100° C. 100°C. 100° C. 100° C. 100° C. 100° C. Torr 100 Torr, 100 Torr, 100 Torr,100 Torr, 100 Torr, 100 Torr, Time 3 Hr 3 Hr 3 Hr 3 Hr 3 Hr 3 Hr Heatingtemperature ° C. 180 180 180 180 180 180 Heating time hour 4 8 6 6 6 6Acid value mgKOH/g 0.15 0.05 0.08 0.05 0.07 0.08 Color hue (YI) 19 22 2221 23 28 MI value g/10 min 15.8 16.0 15.8 15.8 16.3 17.3 Melting point °C. 203.3 203.2 203.5 203.2 203.1 209.3 Tensile strength at kg/cm² 340340 350 340 330 330 break Tensile extension at % 680 690 700 690 700 700break Hidrolysis resistance % 90 100 100 100 100 100 Thermaldecomposition % 80 90 90 90 100 100 Comparative Comparative ComparativeComparative Comparative Comparative Comparative Comparative ExampleExample Example Example Example Example Example Example III-1 III-2III-3 III-4 III-5 III-6 III-7 III-8 TPEE Kind PA-1 PA-1 PA-1 PA-1 PA-1PA-1 PA-1 PA-2 GPE Part by weight 0.9 0.9 1.8 1.8 CE-10 ^(*1) Part byweight 3.0 3.0 3.0 3.0 TPP Part by weight 0.1 0.1 0.1 0.1 0.1 St-Na^(*2) Part by weight 0.1 0.1 0.1 IR ^(*3) Part by weight 0.5 0.5 Meltmixing ° C. 240 260 260 260 260 260 260 260 temperature Melt mixing timeMinute 1.0 2.5 2.5 5.0 5.0 5.0 5.0 5.0 of period Thermal None None NoneNone None None None None None treatment Acid value mgKOH/g 1.10 0.780.52 0.32 0.22 0.11 0.08 0.12 Color hue (YI) 20 26 25 29 28 30 35 41 MIvalue g/10 min 15.4 16.0 16.8 17.2 17.1 16.7 16.3 17.1 Melting point °C. 203.4 203.1 202.0 199.2 198.0 197.5 197.2 200.1 Tensile strengthkg/cm² 340 350 330 300 320 330 320 350 at break Tensile extension % 680690 670 620 640 640 640 610 at break Hydrolysis % 0 0 20 40 50 100 90 90resistance Heat % 50 50 60 70 70 70 90 80 decomposition resistanceExample Example Example Example Example III-7 III-8 III-9 III-10 III-11TPEE Kind PA-1 PA-1 PA-1 PA-1 PA-1 GPE Part by weight 0.45 0.45 0.450.15 0.45 BFDGE ^(*4) Part by weight 0.47 0.47 0.62 0.47 CHDDG ^(*5)Part by weight 0.43 TPP Part by weight 0.1 0.1 0.1 0.1 0.1 St-Na ^(*2)Part by weight IR ^(*3) Part by weight 0.5 0.5 0.5 0.5 PreheatingTemperature 100° C. 100° C. 100° C. 100° C. No preheating Torr 100 Torr,100 Torr, 100 Torr, 100 Torr, Time of period 2 Hr 2 Hr 2 Hr 2 Hr Thermaltreatment ° C. 180 180 180 180 180 temperature Thermal treatment Time ofperiod 10 10 10 10 10 time of period Acid value mgKOH/g 0.15 0.10 0.050.06 0.10 Color hue (YI) 20 23 24 23 25 MI value g/10 min 6.8 5.4 5.81.8 6.5 Melting point ° C. 203.3 203.2 203.5 203.2 203.1 Tensilestrength at break kg/cm² 360 370 350 380 350 Tensile extension at break% 720 710 700 680 720 Hydrolysis resistance % 90 100 100 100 100 Heatdecomposition % 90 100 100 100 100 resistance Melt viscosity stability0.95 0.92 0.98 1.03 1.05 Comparative Comparative Comparative ComparativeComparative Example III-9 Example III-10 Example III-11 Example III-12Example III-12 TPEE Kind PA-1 PA-1 PA-1 PA-1 PA-1 GPE Part by weight0.45 0.90 1.35 1.35 1.35 BFDGE ^(*4) Part by weight 0.47 0.94 0.47 0.470.47 TPP Part by weight 0.1 0.1 0.1 0.1 0.1 IR ^(*3) Part by weight 0.5Melt mixing temperature ° C. 260 260 260 260 260 Melt mixing time ofperiod Minute 5.0 5.0 5.0 5.0 5.0 Thermal treatment None None None NoneNone None time of period Acid value mgKOH/g 0.53 0.25 0.15 0.10 0.17Color hue (YI) 27 26 29 28 32 MI value g/10 min 14.9 10.1 14.6 13.3 15.2Melting point ° C. 197.6 195.2 198.2 198.4 198.2 Tensile strength atbreak kg/cm² 310 280 300 340 330 Tensile extension at break % 680 290710 700 700 Hydrolysis resistance % 20 60 90 100 90 Heat decomposition %60 80 90 90 100 resistance Melt viscosity stability 0.47 Gelation 0.650.69 0.73 CE-10 ^(*1): Kardula E-10, St-Na ^(*2): Sodium stearate, IR^(*3): Irganox 1010, (being common to Tables III-1˜III-4) BFDGE ^(*4):bisphenol F diglycidyl ether, CHDDG ^(*5): diglycidyl cyclohexanedicarboxylate.

In the present invention III, there can be controlled a reaction ratioof the epoxy compound (C) employed by thermally treating the polyesterblock copolymer composition (Q) in a solid phase, and an acid value canbe particularly suppressed in a low level. Whereby, there can beimproved heat resistance and hydrolysis resistance, and there can beprovided the composition (R) having a melt viscosity stability bydecreasing residual epoxy compounds, and which has a more excellentcolor hue compared to a product obtained by conventional methods for thepreparation.

Hereinafter, Examples are illustrated in relation to the presentinvention IV.

Reference Example IV-1

Preparation of a Polyester Block Copolymer (P₁′)

80 parts of a commercially supplied PBT (A₁) and 20 parts ofε-caprolactone (B₁) were fed into the reaction vessel, and a reactionwas conducted at 235° C. for 1 hour while agitating.

Subsequently, pressure was reduced from an ordinary pressure to not morethan 1 torr over 1 hour while maintaining the temperature, and residuale-caprolactone in a system was removed while maintaining a reducedpressure state for further 1 hour.

In the polyester block copolymer (P₁′) obtained, a melting point was185° C., and MI was 11 g/10 minutes.

Reference Example IV-2

Preparation of a Polyester Block Copolymer (P₂′)

85 parts of a commercially supplied PBT (A₂) and 15 parts ofε-caprolactone (B₁) were fed into the vessel, and a reaction wasconducted at 235° C. for 1 hour while agitating.

Subsequently, pressure was reduced from an ordinary pressure to not morethan 1 torr over 1 hour while maintaining the temperature, and residuale-caprolactone in a system was removed while maintaining a reducedpressure state for further 1 hour.

In the polyester block copolymer (P2′) obtained, melting point was 174°C., and MI was 12 g/10 minutes.

Examples IV-1 to IV-24

Polyester block copolymer composition is a compound in which an epoxycompound (C₁ or C₂) having one or more functionalities, an oxalic acidderivative (D₁), salicylic acid derivatives (D₂ and D₃), a hydrazidederivative (D₄), and a variety of stabilizers (E₁ and E₂) are mixed withthe polyester block copolymer (P₁′ or P2′) prepared in the ReferenceExamples IV-1 and IV-2, and heated and kneaded by an extruder.Formulation amount is shown in Table IV-1.

Test pieces were prepared using the polyester block copolymercomposition.

A copper foil having width of 5 mm was spirally wound at a pitch of 5 mminterval between marked lines in the test samples.

Subsequently, the test pieces around which the copper foil is wound wereput between PVC sheets having 30 mm (length)×30 mm (width)×1 mm(thickness) and, further, the PVC sheets in which the test pieces areput between were put between SUS 304-made metal plates having 35 mm(length)×35 mm (width)×3 mm (thickness) to prepare a composite layer.The weight of 5 kgf was placed on the composite layer, followed byplacing in an oven set up at 140° C.

Tensile extension at break was measured in relation to the test piecesplaced in the oven.

Results are shown in Table IV-3. A higher change with a lapse of time inthe tensile extension at break shows a more progressed deterioration.

Comparative Examples IV-1 to IV-7

Likewise as in the Examples IV-1 to IV-24, a polyester block copolymercomposition is a compound in which a variety of additives are mixed withthe polyester block copolymer (P₁′ or P2′) prepared in the ReferenceExamples IV-1 and IV-2, and heated and kneaded by an extruder.Formulation amount is shown in Table IV-1.

In relation to the polyester block copolymer composition, testsaccording to the Example IV-1 were conducted. Results in measurement areshown in Table IV-3.

Comparative Examples IV-8 to IV-13

A polyamide resin having a relative viscosity of 1.80 and a meltingpoint of 178° C. was obtained by adding dodecanoic diacid inpolymerization of a Nylon 12 of Daicel Huels, Ltd. It is to be notedthat the relative viscosity in the polyamide resin was obtained bymeasurement of a solution viscosity in which a 0.5%-metacresol solutionaccording to DIN 53727.

A variety of additives were formulated in the polyamide resin as shownin Table IV-2, followed by compounding to prepare a polyamide resincomposition by an extruder.

In relation to the polyamide resin composition, tests according to theExample IV-1 were conducted. Results in measurement are shown in TableIV-3.

It is to be noted that symbols in the Table IV-1 and the Table IV-2 areas follows.

C₁ Monoglycidylester (Trade name: Kardula E10 manufactured by ShellJapan)

C₂ Diglycidylester (Trade name: Epomic R540 manufactured by MitsuiKagaklu)

D₁ Oxalic acid derivative: bisbenzylidenehydrazide oxalate

D₂ Salicylic acid derivative 1: 3-(salicyloyl)amino-1,2,4-triazole

D₃ Salicylic acid derivative 2: decanedicarboxylic acid disalicyloylhydrazide

D₄ Hydrazide derivative:N,N′-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine

E₁ Stabilizer 1:Tetrakis[methylene-3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate]methane

E₂ Stabilizer 2: organic composite phosphite (Trade name: Advastab(manufactured by Katsuta Kako))

TABLE IV Polyester Polyester block block Epoxy Epoxy Succinic acidSalicylic acid Salicylic acid Hydrazid copolymer copolymer compoundcompound derivative derivative derivative derivative StabilyzerStabilyzer P₁ ¹ P₂ ¹ C₁ C₂ D₁ D₂ D₃ D₄ E₁ E₂ PBW PBW PBW PBW PBW PBW PBWPBW PBW PBW Example IV-1 100 0.6 0.8 0.3 Example IV-2 100 1.0 1.0 0.5Example IV-3 100 0.6 0.8 0.5 0.5 0.5 Example IV-4 100 0.6 0.8 0.3Example IV-5 100 1.0 1.0 0.5 Example IV-6 100 0.6 0.8 0.5 0.5 0.5Example IV-7 100 0.6 0.8 0.3 Example IV-8 100 1.0 1.0 0.5 Example IV-9100 0.6 0.8 0.5 0.5 0.5 Example IV-10 100 0.6 0.8 0.3 Example IV-11 1001.0 1.0 0.5 Example IV-12 100 0.6 0.8 0.5 0.5 0.5 Example IV-13 100 0.60.8 0.3 Example IV-14 100 1.0 1.0 0.5 Example IV-15 100 0.6 0.8 0.5 0.50.5 Example IV-16 100 0.6 0.8 0.3 Example IV-17 100 1.0 1.0 0.5 ExampleIV-18 100 0.6 0.8 0.5 0.5 0.5 Example IV-19 100 0.6 0.8 0.3 ExampleIV-20 100 1.0 1.0 0.5 Example IV-21 100 0.6 0.8 0.5 0.5 0.5 ExampleIV-22 100 0.6 0.8 0.3 Example IV-3 100 1.0 1.0 0.5 Example IV-4 100 0.60.8 0.5 0.5 0.5 C. Ex. IV-1 100 C. Ex. IV-2 100 0.5 C. Ex. IV-3 100 0.50.5 C. Ex. IV-4 100 0.6 0.8 C. Ex. IV-5 100 0.6 0.6 0.5 C. Ex. IV-6 1000.5 C. Ex. IV-7 100 0.5 Poly Salicylic acid Salicyclic acid Salicyclicacid Hydrazide amide Deriv. Deriv. Deriv. Deriv. Stabilizer Stabilizerresin D₁ D₂ D₃ D₄ E₁ E₂ PBW PBW PBW PBW PBW PBW PBW C. Exam. IV-8 100 C.Exam. IV-9 100 0.5 0.5 C. Exam. IV-10 100 0.5 0.5 0.5 C. Exam. IV-11 1000.5 0.5 0.5 C. Exam. IV-12 100 0.5 0.5 0.5 C. Exam. IV-13 100 0.5 0.50.5 Tensile strength at break (%) Placed days 0 5 7 10 14 17 20 23 27 30Example IV-1 485 480 485 460 435 410 390 325 190 50 Example IV-2 470 480480 470 450 390 385 310 160 45 Example IV-3 465 475 470 470 465 440 415370 305 240 Example IV-4 420 435 420 410 400 360 290 210 80 25 ExampleIV-5 415 420 420 395 400 350 265 240 110 25 Example IV-6 420 425 425 420405 390 325 270 200 60 Example IV-7 480 475 470 450 435 400 375 305 17545 Example IV-8 465 460 465 440 435 410 390 290 215 90 Example IV-9 460475 460 445 450 435 405 385 325 215 Example IV-10 420 420 420 390 380360 300 240 120 40 Example IV-11 410 430 400 400 365 370 320 245 135 0Example IV-12 420 425 420 420 405 390 370 345 290 175 Example IV-13 490470 475 470 465 410 355 280 245 80 Example IV-14 480 480 470 455 465 430400 265 205 110 Example IV-15 470 485 480 460 455 450 425 410 385 310Example IV-16 430 415 410 405 400 375 340 295 200 95 Example IV-17 440430 420 400 395 375 350 305 190 100 Example IV-18 435 430 420 420 420405 395 345 300 190 Example IV-19 490 450 440 420 415 395 335 245 120 25Example IV-20 460 440 435 440 440 420 370 275 114.5 25 Example IV-21 460465 460 445 450 430 405 370 360 190 Example IV-22 420 420 425 400 390365 335 275 180 100 Example IV-23 430 430 420 415 410 400 385 290 160 40Example IV-25 420 420 410 410 405 400 390 345 275 170 C. Ex. IV-1 480300 185 0 0 0 0 0 0 0 C. Ex. IV-2 480 450 425 380 375 300 260 125 0 0 C.Ex. IV-3 475 460 430 400 360 280 225 95 0 0 C. Ex. IV-4 490 470 460 390245 90 0 0 0 0 C. Ex. IV-5 485 490 440 410 380 210 75 0 0 0 C. Ex. IV-6480 400 325 220 60 0 0 0 0 0 C. Ex. IV-7 475 415 330 220 135 45 0 0 0 0C. Ex. IV-8 360 50 0 0 0 0 0 0 0 0 C. Ex. IV-9 350 170 45 0 0 0 0 0 0 0C. Ex. IV-10 355 350 300 295 290 160 0 0 0 0 C. Ex. IV-11 360 320 280250 0 0 0 0 0 0 C. Ex. IV-12 330 315 300 315 295 250 0 0 0 0 C. Ex.IV-13 320 325 315 300 220 65 0 0 0 0

The polyester block copolymer composition of the present invention IVhas an excellent heat resistance in contact with a metal and a PVC and,it is preferred as a heat sensitive body to be employed for a heatercode in an electric blanket and electric carpet, and it can be alsoemployed for a long time of period as a heat sensitive body even indirect contact with a metal-made short code or a heating wire and a PVCwhich is an outer cover.

Hereinafter, Examples are illustrated in relation to the presentinvention V.

Comparative Example V-1

60 parts of a PBT (A₁) and 40 parts of ε-caprolactone were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was reduced from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual e-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour.

In the polyester block copolymer obtained, a melting point was 205° C.,and MI was 11 g/10 minutes. It is to be noted that the modulus of strainhardening was not observed.

Comparative Example V-2

30 parts by weight of Celloxide 2021P and 1 part by weight of2-ethyl-4-methylimidazole were formulated with 100 parts of a polyesterblock copolymer obtained in the Comparative Example V-1, followed bycompounding to prepare a composition by a twin screw extruder.

In the composition obtained, an MI was 2 g/10 minutes, and the modulusof strain hardening was not observed.

Reference Example V-1

60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 5% by mol(0.0103 part by weight) of trimethylolpropane were fed into the reactionvessel, and a reaction was conducted at 235° C. for 1 hour whileagitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour to obtain apolyester block copolymer (PA).

In the polyester block copolymer (PA) obtained, a melting point was 194°C., and MI was 2 g/10 minutes, and the modulus of strain hardening wasobserved.

Reference Example V-2

60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 2.-5% by mol(0.0052 part by weight) of trimethylolpropane were fed into the reactionvessel, and a reaction was conducted at 235° C. for 1 hour whileagitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour to obtain apolyester block copolymer (PB).

In the polyester block copolymer (PB) obtained, a melting point was 196°C., and MI was 1 g/10 minutes, and the modulus of strain hardening wasslightly observed.

Reference Example V-3

60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 0.1% by mol(0.206×10⁻³ part by weight) of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was reduced from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour to obtain apolyester block copolymer (PC).

In the polyester block copolymer (PC) obtained, a melting point was 194°C., and MI was 5 g/10 minutes, and the modulus of strain hardening wasslightly observed.

Examples V-1 to V-11

A polyester block copolymer composition was prepared by formulating andcompounding through heating and kneading an epoxy compound having one ormore functionalities and a carbodiimide compound by an extruder with thepolyester block copolymers prepared in the Reference Examples V-1 to V-3at a ratio shown in Table V-1 to measure the modulus of strainhardening. Results are shown in Table V-1.

Further, test pieces and conditioned test pieces were prepared using thepolyester block copolymer compositions, and tensile extension at breakwas measured in relation to the conditioned test pieces. Results areshown in Table V-2.

A higher change ratio of the tensile extension at break with a lapse oftime shows a more progressed deterioration.

Comparative Example V-3

60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 150% by mol(0.309 parts by weight) of trimethylolpropane were fed into a reactionvessel, and a reaction was conducted at 235° C. for 1 hour whileagitating. Subsequently, pressure was reduced from an ordinary pressureto not more than 1 torr over 1 hour while maintaining the temperature,and residual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour to obtain a polyester blockcopolymer.

In the polyester block copolymer obtained, a melting point was 179° C.which was fairly lowered, and MI was 2 g/10 minutes, and the modulus ofstrain hardening was observed.

Comparative Examples V-4 to V-6

Likewise as in the Examples V-1 to V-11, a polyester block copolymercomposition was prepared by formulating and compounding through heatingand kneading a variety of additives by a twin-screw extruder with thepolyester block copolymer prepared in the Reference Examples V-1 to V-3.Formulation amount is shown in Table V-1. In relation to the polyesterblock copolymer composition, tests were conducted according to theExamples V-1 to V-11. Results in measurement are shown in Table V-2.

TABLE V Polyester Polyester Polyester Epoxy Epoxy Carbodiimide Modulusblock copolymer block copolymer block copolymer compound compoundcompound Stabilizer Stabilizer of (PA) (PB) (PC) C1 C2 E1 F1 F2 Strain-PBW PBW PBW PBW PBW PBW PBW PBW hardening Exam. V-1 100 0.6 0.8 ⊚ Exam.V-2 100 1.0 1.0 ⊚ Exam. V-3 100 0.6 0.8 0.5 ⊚ Exam. V-5 100 0.6 0.8 ⊚Exam. V-6 100 1.0 1.0 ⊚ Exam. V-7 100 0.6 0.8 0.5 ⊚ Exam. V-8 100 0.60.8 0.5 0.5 ⊚ Exam. V-9 100 0.6 0.8 0.5 ◯ Exam. V-10 100 1.0 1.0 0.5 ◯Exam. V-11 100 0.6 0.8 0.5 0.5 0.5 ◯ C. Ex. V-4 100 5.0 5.0 Gel C. Ex.V-5 100 5.0 5.0 Gel C. Ex. V-6 100 0.5 0.1 0.5 0.5 X Tensile extensionat break (%) Placed days 0 5 7 10 14 17 20 23 27 30 Example V-1 420 435420 410 400 360 290 210 80 25 Example V-2 415 420 420 395 400 350 265240 110 25 Example V-3 480 475 470 450 435 400 375 305 175 45 ExampleV-4 420 425 425 420 405 390 325 270 200 60 Example V-5 470 480 480 470450 390 385 310 160 45 Example V-6 485 480 485 460 435 410 390 325 19050 Example V-7 460 475 460 445 450 435 405 385 325 215 Example V-8 465460 465 440 435 410 390 360 330 260 Example V-9 490 495 490 490 485 460370 220 160 55 Example V-10 495 510 515 515 510 480 440 400 350 250Example V-11 480 485 480 480 475 460 420 400 370 340 C. Example V-1 480300 185 0 0 0 0 0 0 0 C. Example V-2 480 475 475 460 435 400 360 305 19060 C. Example V-3 475 350 200 0 0 0 0 0 0 0 C. Example V-6 460 470 460440 430 400 370 330 290 200 C1: monoglycidylester of versatic acid(trade name: Kardula E10 manufactured by Shell Japan) C2:diglycidylester of cyclohexane dicarboxylic acid (trade name: EpomicR540 manufactured by Mitsui Kagaku) E1: carbodiimide compound: Stabaxol(manufactured by Sumitomo Bayer Urethane) F1: stabilizer 1:tetraxis[methylene-3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate]methaneF2: stabilizer 2: organic complexed phosphite (trade name: Advastabmanufactured by Katsuta Kako) *⊚ the presence of modulus of strainhardening (slope is not less than 1.0 in the above-described definition)◯ minor modulus of strain hardening (slope is less than 1.0 in theabove-described definition) X the absence of modulus of strain hardening(slope is 0 in the above-described definition) Gel: many gels

It is large in dependence upon extension rate, and provides a moldedarticle having uniform thickness in blow molding and, further, it has acharacteristic of exceedingly less flashes in molding. Moreover, amolded article obtained from a composition is very excellent in heatresistance in addition to properties inherently possessed by a polyesterblock copolymer. It does not cause a thermal deterioration even beingemployed for a use exposed to a high temperature for a long time ofperiod, and it provides a molded article having very excellent physicalproperties.

Hereinafter, Examples are illustrated in relation to the presentinvention VI.

Reference Example VI-1

(Preparation of a Polyester Block Copolymer (P-A))

60 parts of a PBT (A₁), 40 parts of e-caprolactone, and 150% by mol of2,4-dihydroxy benzoate based on 100% by mol of polybutylene phthalatewere fed into a reaction vessel, and a reaction was conducted at 235° C.for 1 hour while agitating.

Subsequently, pressure was reduced from an ordinary pressure to not morethan 1 torr over 1 hour while maintaining the temperature, and residualε-caprolactone in a system was removed while maintaining a reducedpressure state for further 1 hour. In the polyester block copolymerobtained, a melting point was 190° C., and MI was 2 g/10 minutes.Further, the modulus of strain hardening was observed. The polyesterblock copolymer was designated as Copolymer (P-A).

Reference Example VI-2

(Preparation of a Polyester Block Copolymer (P-B))

60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 50% by mol of2,4-dihydroxy benzoate based on 100% by mol of a polybutylene phthalatewere fed into a reaction vessel, and a reaction was conducted at 235° C.for 1 hour while agitating.

Subsequently, pressure was reduced from an ordinary pressure to not morethan 1 torr over 1 hour while maintaining the temperature, and residualε-caprolactone in a system was removed while maintaining a reducedpressure state for further 1 hour. In the polyester block copolymerobtained, a melting point was 199° C., and MI was 4 g/10 minutes.Further, the modulus of strain hardening was observed. The polyesterblock copolymer was designated as Copolymer (P-B).

Reference Example VI-3

(Preparation of a Polyester Block Copolymer (P-C))

60 parts of a PBT (A₁), 40 parts of e-caprolactone, and 0.1% by mol of2,4-dihydroxy benzoate based on 100% by mol of polybutylene phthalatewere fed into a reaction vessel, and a reaction was conducted at 235° C.for 1 hour while agitating.

Subsequently, pressure was decreased from an ordinary pressure to notmore than 1 torr over 1 hour while maintaining the temperature, andresidual e-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour. In the polyester blockcopolymer obtained, a melting point was 205° C., and MI was 5 g/10minutes. Further, the modulus of strain hardening was observed. Thepolyester block copolymer was designated as Copolymer (P-C).

Examples VI-1 to VI-11

Polyester block copolymer composition was prepared by formulating andcompounding through heating and kneading an epoxy compound having one ormore functionalities and a carbodiimide compound by an extruder with thepolyester block copolymers (P-A), (P-B), and (P-C) prepared in theReference Examples VI-1 to VI-3.

Formulating amount and the presence or absence of the modulus of strainhardening are shown in Table VI-1.

Further, test pieces and conditioned test pieces were prepared using thepolyester block copolymer compositions, and tensile extension at breakwas measured in relation to the conditioned test pieces. Results areshown in Table VI-2. A higher change ratio of the tensile extension atbreak with a lapse of time shows a more progressed deterioration.

Comparative Example VI-1

60 parts of a PBT (A₁) and 40 parts of ε-caprolactone were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 205° C., and MIwas 11 g/10 minutes. The modulus of strain hardening was not observed.

Comparative Example VI-2

30 parts by weight of Celloxide 2021P and 1 part by weight of2-ethyl-4-methylimidazole were formulated with 100 parts of a polyesterblock copolymer obtained in the Comparative Example VI-1, followed bycompounding to prepare a composition by an extruder. In the compositionobtained, an MI was 2 g/10 minutes, and the modulus of strain hardeningwas not observed.

Comparative Example VI-3

60 parts of a PBT (A₁), 40 parts of ε-caprolactone, and 300% by mol of2,4-dihydroxy benzoate based on 100% by mol of a polybutylene phthalatewere fed into a reaction vessel, and a reaction was conducted at 235° C.for 1 hour while agitating.

Subsequently, pressure was decreased from an ordinary pressure to notmore than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour. In the polyester blockcopolymer obtained, a melting point was 179° C. which is fairly lowered,and MI was 1 g/10 minutes. The modulus of strain hardening was observed.

Comparative Examples VI-4 to VI-6

Likewise as in the Examples VI-1 to VI-11, polyester block copolymercomposition was prepared by formulating and compounding through heatingand kneading a variety of additives by an extruder with the polyesterblock copolymers (P-A), (P-B), and (P-C) prepared in the ReferenceExamples VI-1 to VI-3. Formulating amount is shown in Table VI-1. Inrelation to the polyester block copolymer compositions, tests wereconducted according to the Examples VI-1 to VI-11. Results inmeasurement are shown in Table V-2.

TABLE VI Polyester Polyester Polyester Epoxy Epoxy Stabi- Stabi- Modulusblock copolymer block copolymer block copolymer Compound CompoundCarbodimide lizer lizer of (P-A) (P-B) (P-C) 1¹⁾ 2²⁾ Compound³⁾ 1⁴⁾ 2⁵⁾Strain- PBW PBW PBW PBW PBW PBW PBW PBW hardening⁶⁾ Exam. VI-1 100 0.60.8 ⊚ Exam. VI-2 100 1.0 1.0 ⊚ Exam. VI-3 100 0.6 0.8 0.5 ⊚ Exam. VI-4100 0.6 0.8 0.5 0.5 ⊚ Exam. VI-5 100 0.6 0.8 ⊚ Exam. VI-6 100 1.0 1.0 ⊚Exam. VI-7 100 0.6 0.8 0.5 ⊚ Exam. VI-8 100 0.6 0.8 0.5 0.5 ⊚ Exam. VI-9100 0.6 0.8 0.5 ◯ Exam. VI-10 100 1.0 1.0 0.5 ◯ Exam. VI-11 100 0.6 0.80.5 0.5 0.5 ◯ C. Ex. VI-4 100 5.0 5.0 Gel C. Ex. VI-5 100 5.0 5.0 Gel C.Ex. VI-6 100 0   0   0.5 0.5 0.5 X Tensile extension at break (%) Placeddays 0 5 7 10 14 17 20 23 27 30 Example VI-1 440 440 430 420 400 360 290210 80 30 Example VI-2 415 420 420 395 380 360 310 240 110 30 ExampleVI-3 450 470 470 450 435 400 375 305 175 45 Example VI-4 420 425 425 420405 390 370 330 270 205 Example VI-5 480 480 480 470 450 390 385 310 16045 Example VI-6 460 470 470 460 435 410 390 325 190 50 Example VI-7 460475 460 450 450 435 405 385 310 205 Example VI-8 430 445 450 440 435 410380 350 310 260 Example VI-9 490 495 490 490 485 460 370 220 160 60Exam. VI-10 495 510 515 515 510 470 430 370 300 220 Exam. VI-11 480 485480 480 475 450 410 365 310 250 C. Exam. VI-1 480 300 185 0 0 0 0 0 0 0C. Exam. VI-2 480 475 475 460 435 400 360 305 190 60 C. Exam. VI-3 475350 200 0 0 0 0 0 0 0 C. Exam. VI-6 460 470 460 440 430 400 370 330 290200 ¹⁾ monoglycidyl ester (Trade name: Kardula E10 (manufactured byShell Japan)) ²⁾ diglycidyl ester (Trade name: Epomik R540 (manufacturedby Mitsui Kagaku)) ³⁾ carbodiimide compoud: Stabaxol 1 (manufactured bySumitomo Baier Urethane) ⁴⁾ Stabilizer 1:tetrakis[methylene-3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate]methane⁵⁾ Stabilizer 2: organic complexed phosphoric salt (Trade name: Advastab(manufactured by Katsuta Kako)) ⁶⁾⊚: the presnce of strain-hardeningproperty, ◯: the presnce of slight strain-hardening property, X: theabesnce strain-hardening property, Gel: a large amount of gel

Since the composition by the present invention VI has the modulus ofstrain hardening, it is supposed that there can be obtained a moldedarticle having uniform thickness in blow molding and, moreover, sincethe molded article has a low change ratio of the tensile extension atbreak with a lapse of time, there can be obtained a polyester blockcopolymer composition having a lower deterioration with a lapse of time.A molded article obtained using the composition is very excellent inheat resistance in addition to properties inherently possessed by apolyester block copolymer, and the molded article does not cause athermal deterioration even being employed for a use exposed to a hightemperature for a long time of period.

Hereinafter, Examples are illustrated in relation to the presentinvention VII.

Preparation Example VII-1

60 parts of a polybutylene terephthalate (A₁), 40 parts ofε-caprolactone, and 150% by mol of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was reduced from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 190° C., and anumber average molecular weight was 56000.

The copolymer is designated as Polyester block copolymer (P-A).

Preparation Example VII-2

60 parts of a polybutylene terephthalate (A₁), 40 parts ofε-caprolactone, and 50% by mol of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 199° C., and anumber average molecular weight was 61000. The copolymer is designatedas Polyester block copolymer (P-B).

Preparation Example VII-3

60 parts of a polybutylene terephthalate (A₁), 40 parts ofε-caprolactone, and 0.1% by mol of trimethylolpropane were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was reduced from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 205° C., and anumber average molecular weight was 71200. The copolymer is designatedas Polyester block copolymer (P-C).

Preparation Example VII-4

60 parts of a polybutylene terephthalate (A₁), 40 parts ofε-caprolactone, and 150% by mol of 2,4-dihydroxy benzoate were fed intoa reaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 190° C., and anumber average molecular weight was 51000. The copolymer is designatedas Polyester block copolymer (P-D).

Preparation Example VII-5

60 parts of a polybutylene terephthalate (A₁), 40 parts ofε-caprolactone, and 80% by mol of 2,4-dihydroxy benzoate were fed into areaction vessel, and a reaction was conducted at 235° C. for 1 hourwhile agitating. Subsequently, pressure was decreased from an ordinarypressure to not more than 1 torr over 1 hour while maintaining thetemperature, and residual ε-caprolactone in a system was removed whilemaintaining a reduced pressure state for further 1 hour. In thepolyester block copolymer obtained, a melting point was 200° C., and anumber average molecular weight was 63800. The copolymer is designatedas Polyester block copolymer (P-E).

Preparation Example VII-6

60 parts of a polybutylene terephthalate (A₁) having a melting point of230° C., 40 parts of ε-caprolactone, and 0.5% by mol of 2,4-dihydroxybenzoate were fed into a reaction vessel, and a reaction was conductedat 235° C. for 1 hour while agitating.

Subsequently, pressure was decreased from an ordinary pressure to notmore than 1 torr over 1 hour while maintaining the temperature, andresidual ε-caprolactone in a system was removed while maintaining areduced pressure state for further 1 hour. In the polyester blockcopolymer obtained, a melting point was 204° C., and a number averagemolecular weight was 69100. The copolymer is designated as Polyesterblock copolymer (P-F).

Preparation Example VII-7

60 parts of a polybutylene terephthalate (A₁) and 40 parts ofε-caprolactone were fed into a reaction vessel, and a reaction wasconducted at 235° C. for 1 hour while agitating. Subsequently, pressurewas decreased from an ordinary pressure to not more than 1 torr over 1hour while maintaining the temperature, and residual ε-caprolactone in asystem was removed while maintaining a reduced pressure state forfurther 1 hour. In the polyester block copolymer obtained, a meltingpoint was 204° C., and a number average molecular weight was 76500.

The copolymer is designated as Polyester block copolymer (P-G).

Preparation Example VII-8

60 parts of a polybutylene terephthalate (A₁) having a melting point of230° C., 40 parts of ε-caprolactone, and 300% by mol of 2,4-dihydroxybenzoate were fed into a reaction vessel, and a reaction was conductedat 235° C. for 1 hour while agitating. Subsequently, pressure wasreduced from an ordinary pressure to not more than 1 torr over 1 hourwhile maintaining the temperature, and residual ε-caprolactone in asystem was removed while maintaining a reduced pressure state forfurther 1 hour. In the polyester block copolymer obtained, a meltingpoint was 179° C. which is fairly lowered. As described hereinabove,when a multifunctional compound is added in a large amount, a meltingpoint is largely lowered.

Examples VII-1 to VII-10

Polyester block copolymer composition is a mixture in which compoundsselected from cyclohexane diglycidylester (CHDGE), Kardular E10, sodiumstearate, and Irganox 1010 are mixed with 100 parts by weight of thepolyester block copolymers prepared in the Preparation Examples VII-1 toVII-6 in the weight part described in Table VII-1, respectively, andwhich is prepared by agitating at room temperature for 30 minutes in adrum tumbler. The mixture was extruded using a 32 mmø twin screwextruder at 230° C. for a heating time of period of 2.5 minutes, and cutand pelletized after cooled in water.

Pellets obtained were fed into a tank type apparatus which can be heatedand agitated, and can be pressure-reduced and purged by nitrogen, andpreheated under conditions of 100° C. and 100 torr for 3 hours. Further,the apparatus was purged by nitrogen and returned to an ordinarypressure, and a thermal treatment was conducted by elevating to 180° C.After the treatment, it was cooled under a nitrogen atmosphere to takeout pellets, and there were measured an MI value, a tensile strength andextension, a melting point, color hue, an acid value, a number averagemolecular weight, the modulus of strain hardening, and a draw-downproperty. Conditions for measurement and results are shown in TableVII-2.

As sown in the Tables VII-1 and VII-2, by the method of the presentinvention, there can be obtained resins having an excellent draw-downproperty and color hue and, in which an acid value can be reduced by asmall amount of the epoxy compounds, in which decline of viscosity isless, and which have excellent physical properties.

Further, the mount of volatile components was less in melt-mixingcompared to the Comparative Examples as described hereinafter.

Comparative Examples VII-1 to VII-7

Polyester block copolymer composition is a mixture in which compoundsselected from the CHDGE, Kardular E10, sodium stearate, and Irganox 1010are mixed with the polyester block copolymers prepared in thePreparation Examples VII-1 to VII-7 in the weight part described inTable VII-1, respectively, and which is prepared by agitating at roomtemperature for 30 minutes in a drum tumbler.

The mixture was extruded using a 32 mmø twin screw extruder at atemperature and time of period adjusted as shown in Table VII-1 andwhile controlling an feeding amount, and cut and pelletized after cooledin water.

In relation to the pellets obtained, there were measured an MI value, atensile strength and extension, a melting point, color hue, an acidvalue, a number average molecular weight, the modulus of strainhardening, and a draw-down property. Conditions for measurement andresults are shown in Table VII-2.

As shown in the Tables VII-1 and VII-2, it is confirmed that althoughthe draw-down property is partially observed, a level is small, anddraw-down resistance is also small which is required in blow molding.Further, it is confirmed that a large amount of epoxy compounds arerequired in order to sufficiently lower an acid value, and there becomeworse physical properties such as color hue and viscosity.

Comparative Example VII-8

A composition was prepared by compounding using a twin screw extruderafter formulating 30 parts by weight of Celloxide 2021 and 1 part byweight of 2-phenylimidazole with the polyester block copolymer obtainedin the Preparation Example VII-7. In relation to the compositionobtained, there were measured an MI value, a tensile strength andextension, a melting point, color hue, an acid value, a number averagemolecular weight, the modulus of strain hardening, and a draw-downproperty. Conditions for measurement and results are shown in TableVII-2. The modulus of strain hardening was not observed.

Comparative Examples VII-9 to VII-11

Likewise as in the Examples VII-1 to VII-10, a polyester block copolymercomposition is a mixture in which compounds selected from the CHDGE,Kardular E-10, sodium stearate, and Irganox 1010 are mixed with 100parts by weight of the polyester block copolymer prepared in thePreparation Example VII-7 in the weight part described in Table,respectively, which is prepared by agitating at room temperature for 30minutes in a drum tumbler. The mixture was extruded using a 32 mmø twinscrew extruder at 230° C. and a heating time of period of 1 minute, andcut and pelletized after cooled in water.

Pellets obtained were fed into a tank type apparatus which can be heatedand agitated and can be pressure-reduced and purged by nitrogen, and athermal pretreatment was conducted at conditions of 100° C. and 100 torrfor 3 hours. Further, a thermal treatment was conducted at 180° C. afterhaving returned to an ordinary pressure by purging nitrogen. Aftercooled under nitrogen, and pellets were taken out to measure an MIvalue, a tensile strength and extension, a melting point, color hue, anacid value, a number average molecular weight, a modulus of strainhardening, and a draw-down property. Conditions for measurement andresults are shown in Table VII-2. The modulus of strain hardening wasnot observed in all samples.

TABLE VII Melt Polyester Mixing Melt Heating block Kardula SodiumIrganox Tempera- Mixing Tempera- Heating Copolymer CHDGE E10 Stearate1010 ture Time ture Time Kind PBW PBW PBW PBW ° C. minute ° C. Hour C.Ex. VII-1 (A) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex. VII-2 (B) 1.8 0.7 0.10.5 260 2.5 — — C. Ex. VII-3 (C) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex.VII-4 (D) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex. VII-5 (E) 1.8 0.7 0.1 0.5260 2.5 — — C. Ex. VII-6 (F) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex. VII-7(G) 1.8 0.7 0.1 0.5 260 2.5 — — C. Ex. VII-8 (G) — — 0.1 0.5 260 2.5 — —C. Ex. VII-9 (G) 0.3 1.5 0.1 0.5 240 2.5 180 8 C. Ex. VII-10 (G) 0.5 1.50.1 0.5 240 2.5 180 8 C. Ex. VII-11 (G) 0.7 1.5 0.1 0.5 240 2.5 180 8Exam. VII-1 (A) 0.7 1.5 0.1 0.5 240 2.5 180 8 Exam. VII-2 (B) 0.3 1.50.1 0.5 240 2.5 180 8 Exam. VII-3 (B) 0.5 1.5 0.1 0.5 240 2.5 180 8Exam. VII-4 (B) 0.7 1.5 0.1 0.5 240 2.5 180 8 Exam. VII-5 (C) 0.7 1.50.1 0.5 240 2.5 180 8 Exam. VII-6 (D) 0.7 1.5 0.1 0.5 240 2.5 180 8Exam. VII-7 (E) 0.3 1.5 0.1 0.5 240 2.5 180 8 Exam. VII-8 (E) 0.5 1.50.1 0.5 240 2.5 180 8 Exam. VII-9 (E) 0.7 1.5 0.1 0.5 240 2.5 180 8Exam. VII-10 (F) 0.7 1.5 0.1 0.5 240 2.5 180 8 MIV AV CH g/10 MP TSABTEAB HR HTR NAMW mgKOH/g (YI) min ° C. kg/cm² % % % MVS MSH DDP Mn C.Ex. VII-1 0.1 22 4.1 178 490 700 100 100 1.2 0.6 2.0 65000 C. Ex. VII-20.1 22 4.8 188 450 710 100 100 1.1 0.4 1.8 69500 C. Ex. VII-3 0.1 23 6.7190 490 680 100 100 1.1 0.2 1.6 73300 C. Ex. VII-4 0.1 20 5.0 182 450650 100 100 0.7 0.7 2.2 64000 C. Ex. VII-5 0.1 18 7.1 192 470 650 100100 0.9 0.5 2.1 67800 C. Ex. VII-6 0.1 23 8.5 196 470 660 100 100 1.00.2 1.8 70100 C. Ex. VII-7 0.1 19 5.2 197 490 690 100 100 1.1 0   1.579000 C. Ex. VII-8 0.3 32 2.1 188 480 700  70  80 0.7 0   3.5 73200 C.Ex. VII-9 0.1 16 1.7 203 440 680 100 100 1.0 0   3.8 78500 C. Ex. VII-100.1 15 1.4 203 470 670 100 100 1.0 0   4.0 81000 C. Ex. VII-11 0.1 150.9 202 450 680 100 100 1.0 0   4.5 84400 Exam. VII-1 0.1 16 0.8 189 490700 100 100 1.0 1.4 4.6 69900 Exam. VII-2 0.1 16 1.9 198 490 660 100 1001.0 0.5 3.5 67700 Exam. VII-3 0.1 14 1.6 198 420 700 100 100 1.0 0.7 3.871000 Exam. VII-4 0.1 15 1.1 199 470 690 100 100 1.0 0.9 4.2 74200 Exam.VII-5 0.1 15 0.9 204 460 710 100 100 1.0 0.5 4.3 76100 Exam. VII-6 0.117 0.8 190 480 640 100 100 0.9 1.6 4.4 72300 Exam. VII-7 0.1 18 2.2 200450 690 100 100 0.9 0.6 3.2 65100 Exam. VII-8 0.1 18 1.5 201 480 690 100100 0.9 1.0 3.9 67000 Exam. VII-9 0.1 19 0.8 201 480 700 100 100 0.9 1.24.4 77000 Exam. VII-10 0.1 16 0.9 205 480 670 100 100 0.9 0.6 4.2 77100In the Table VII, the abbreviation “PBW” means “part by weight”. In theTable VII, abbreviations are follows. AV: acid value, CH: color hue,MIV: MI value, MP: melting point, TSAB: tensile strength at break TEAB:tensile extension at break, HR: hydrolysis resistance, HTR: MVS: MSH:DDP: NAMW:

By the present invention, there can be obtained a polyester blockcopolymer composition having an excellent moldability by which it can beapplied in blow molding and a variety of molding processes without anyhindrance, and which has an excellent heat resistance and rubberyelasticity.

What is claimed is:
 1. A method for the preparation of a polyester blockcopolymer (P1) characterized in that in the method for the preparationof 100% by weight of the polyester block copolymer (P1) by allowing toreact A% by weight of a crystalline aromatic polyester (A1) with B% byweight of lactones (B) (A+B=100), not less than (B+0.5)% by weight ofthe lactones (B) are introduced into A% by weight of the crystallinearomatic polyester (A1), and reaction is terminated at a period when notless than 0.5% by weight of unreacted lactones remain with respect to100% by weight of the polyester block copolymer (P1) after preparationof the copolymer, and then the unreacted lactones are removed at a solidphase.
 2. A method for the preparation of a polyester block copolymer(P1) as claimed in claim 1, wherein not less than (B+2.5)% by weight ofsaid lactones (B) are introduced and reaction is terminated at a periodwhen not less than 2.5% by weight of unreacted lactones remain withrespect to 100% by weight of said polyester block copolymer (P1) afterpreparation of the copolymer.
 3. A method for the preparation of apolyester block copolymer (P1) as claimed in claim 1 or claim 2, whereinthe reaction proportion (A)/(B) of said crystalline aromatic polyester(A1) with respect to said lactones (B) is between 95/5 and 20/80 byweight.
 4. A method for the preparation of a polyester block copolymer(P1) as claimed in claim 1 or claim 2, wherein said crystalline aromaticpolyester (A1) and said lactones (B) are continuously supplied into areaction vessel and addition-polymerized, and said polyester blockcopolymer (P1) is continuously taken out.
 5. A method for thepreparation of a polyester block copolymer (P1) as claimed in claim 3,wherein said crystalline aromatic polyester (A1) and said lactones (B)are continuously supplied into a reaction vessel andaddition-polymerized, and said polyester block copolymer (P1) iscontinuously taken out.
 6. A method for the preparation of a polyesterblock copolymer (P1) as claimed in claim 4, wherein said unreactedlactones are continuously removed.
 7. A method for the preparation of apolyester block copolymer (P1) as claimed in claim 5, wherein saidunreacted lactones are continuously removed.
 8. A method for thepreparation of a polyester block copolymer (P1) as claimed in claim 1 orclaim 2, wherein said crystalline aromatic polyester (A1) is apolybutylene terephthalate.
 9. A method for the preparation of apolyester block copolymer (P1) as claimed in claim 1 or claim 2, whereinsaid lactones (B) are caprolactone.
 10. A method for the preparation ofa polyester block copolymer (P′1) having a high molecular weightcharacterized in that a polycondensation reaction is further conductedin the solid phase after having prepared said polyester block copolymer(P1) according to claim 1 or claim
 2. 11. A method for the preparationof a polyester block copolymer (P′1) having a high molecular weight asclaimed in claim 10, wherein said reaction in the solid phase iscontinuously conducted.